Contribution to the understanding effects of weak electrical phenomena

doi:10.4236/ns.2010.211148

Vol.2, No.11, 1195-1210 (2010) Natural Science

http://dx.doi.org/10.4236/ns.2010.211148

Contribution to the understanding effects of weak

electrical phenomena

Józef Mazurkiewicz, Piotr Tomasik*

Department of Chemistry and Physics, University of Agriculture, Balicka Street 122, 30 049 Kraków, Poland; *Corresponding author:

[email protected]

Received 21 June 2010; revised 25 July 2010; accepted 29 July 2010.

ABSTRACT

Electronic emission spectra of N2, (N2)2, (N2)5 O2,

(O2)2, (O2)5, H2O, (H2O)5, CO2, (CO2)2, CO2..H2O,

NH3 and NH3.H2O situated in the electric field of

0.001, 0.005, 0.01 0.05 and 0.1 a.u. were simu-

lated involving Monte Carlo optimization fol-

lowed by the ZINDO/S approach. The simulated

spectra showed irregular dependence on the

energy of the electric field applied. Molecules

without influence of the electric field emit in the

vacuum ultraviolet region. Applied electric field

only in case of (O2)5 generated transitions above

200 nm. The mapping of isosurface of the in-

vestigated molecules revealed that the electric

field applied redistributed the charge densities

in the molecules in the manner approximately

parallel to the energy of the field. Applied elec-

trical field resulted in an increase in the water

acidity and ammonia basicity.

Keywords: Electronic Emission Spectra; Surface

Effect; ZINDO/S Spectra Simulations

1. INTRODUCTION

There are numerous papers (see, for instance [1]) de-

scribing the effect of electromagnetic field upon bio-

logical systems. Particular attention has been paid to

electrostimulation of the alcoholic fermentation [2,3].

Electric current changed the fermentation characteristics

of yeast. Either the 10 mA direct current (DC) or 100

mA alternating current (AC) applied to the culture broth

significantly increased the cell growth and alcohol pro-

duction rate. Also accompanied formation of higher al-

cohols, esters and organic acids was influenced in such

manner although some of them could result from the

anodic oxidation of ethanol. Since the phenomena ob-

served in the case of electrostimulation were observed in

the wort likely the effect could not be assisted by the

effect of the external field. Nechitailo and Gordeev [4]

related observed effect of an artificial electric field upon

growth of plants to perturbations occurred on the plant

cell membranes.

Another electrical phenomenon known as corona dis-

charges have found several practical applications [5,6].

Corona discharges (Saint Elmo’s fire) have a straight-

forward physical background [5,7-14]. Recent studies on

the effect of corona discharges on granular starch [15]

showed that, in contrast to other solid material such as

metals and plastics, it penetrated starch granules causing

depolymerization of polysaccharides in the granule inte-

rior. Liu and Zou [16] presented hydrolysis of starch to

mono- and di-saccharides with dielectric barrier dis-

charge plasma. They showed that proton layer was

formed within the steam layer. Recently, a series of pa-

pers on modification of carbon nanotubes with low-

temperature glow plasma was published [17-20]. Elec-

trical field could be used for regulation of viscosity of

liquids and, hence, their flow (see, for instance [21]).

There are also weaker electric phenomena which, al-

though common, did not find sufficient appreciation.

They result from the effect of the surface. Atoms local-

ized inside any solid and liquid structure are in different

energetic situation than these situated on the surface of

these structures i.e. on the phase borderlines. Atoms lo-

calized on the surface of the structures, particularly on

sharp edges and tips of needles dispose with some ex-

cessive energy as their interactions with elements of an-

other phase, especially gaseous, are weaker. Such cir-

cumstances are responsible for well known catalytic

effects of the surface, effect of lightning rod and so on.

The non-saturation of interactions of the peripheral at-

oms generate a gradient of potential and, in consequence,

the electromagnetic field around the object. Molecules

residing in this thin layer interact with the surface and

with one another. Energy of such molecules is, addition-

ally, influenced by external electric field to the extent

J. Mazurkiewicz et al. / Natural Science 2 (2010) 1195-1210

1196

which might be reflected in their electronic spectra.

Electromagnetic field is a volume of space around the

object in which energy particles called photons can mi-

grate either from that object into the space or from the

space to that object causing a ionization. In such manner

a cold plasma is formed. Properties of the molecules in

such plasma remain unknown.

In this paper evaluation of differences between mole-

cules outside and inside plasma surrounding the surface

of inanimate objects is carried out involving electronic

emission spectra of simple small molecules as nitrogen,

oxygen, water, carbon dioxide and ammonia are simu-

lated when placed in an electric field and without appli-

cation of that field.

There are available in the literature electronic spectra

of the same molecules covering the region from 200 to

20 nm and these spectra have been computed with more

advanced methods [22-24] but the spectra of these

molecules in the electric field are lacking. In this paper,

for diagnostic purposes of the effect of the electric field

upon the structure of the molecules spectra were calcu-

lated using less sophisticated ZINDO/S [25] method

which was specially designed by its inventor for simula-

tion of the spectra in the UVVIS region.

2. COMPUTATIONS

Applying the Monte Carlo method [26] single

molecules of N2, O2 (considered as biradical), water, CO2,

CO2 with water, ammonia and ammonia in water were

brought to temperature of 300 K and with influence of

electric field of 0.01 a.u (and electronic spectra were

simulated with HyperChem 8.0 involving ZINDO/S

semiempirical method. These computations were also

performed for 2 and 5 molecules of N2 and O2, 2

molecules of CO2 and 5 molecules of water and,

additionally, for single molecules of N2 and O2 in the

one-direction electric field varying between 0.005 and

0.1 a.u. (1 a.u. = 1.49x10-10 J = 931 MeV)

Visualization of the iusosurface was performed with

HyperChem 8, Plot Molecular Graphs, 3D Mapped

Isosurface.

3. RESULTS AND DISCUSSION

Because of the surface effect, the UV spectra of

molecules present in aura surrounding surface of the

matter should somehow differ from the spectra of the

molecules over the region of aura. Changes in the mo-

lecular structure induced by external electric field could

be available and visualized in form of electronic spectra

simulated involving suitable software. This study should

be understood as an approach to the recognition of the

effect of electric field upon non-recordable plasma (aura)

residing on the surface of inanimate objects.

Table 1 presents results of the computations carried

out for nitrogen molecules.

Computations for small diatomic symmetric molecule

Table 1. Simulated electronic spectra of one, two and five nitrogen molecules without exposure and with exposure to external

electric field.

Transition energy (E) [nm] and its characteristicsa

Without electric field With electric field

Molecule

(total number

of transitions) E fb

Orbital → orbital

(HOMO → LUMO)

and total energy [a.u]

E fb

Orbital → orbital

(HOMO → LUMO)

and total energy [a.u.]

N2

(30)

100.2

90.8

56.9

23.6

0.2528

0.8100

1.2466

0.4178

1→15, 2→6

1→16, 2→7

1→17, 4→7

1→23, 5→8

1→31, 1→8

–16.514669174

100.0c

100.0

90.0

57.0

51.7

23.5

0.2520

0.8029

1.2217

0.0001

0.4003

1→15; 2→6

1→16; 2→7

1→17; 4→6, 3→7

1→23; 5→8

1→25; 2→8

1→31; 1→8

–16.531251288

175.0d

175.0

174.7

100.2

90.6

56.9

51.7

23.6

0.0001

0.2525

0.8087

1.2398

0.0028

0.4150

1→9, 5→7

1→10, 5→6

1→11, 5→7, 4→6, 3→7

1→12, 5→6, 4→7, 3→6

1→15, 2→6

1→16, 2→7

1→17, 4→6, 3→7

1→23, 5→8

1→25, 2→8

1→31, 1→8

–16.517425927

175.4e

175.4

174.8

0.0003

1→9, 5→7, 4→6

1→10, 5→6, 4→7

1→11, 5→7, 4→6, 3→7

1→12, 5→6, 4→7, 3→6

J. Mazurkiewicz et al. / Natural Science 2 (2010) 1195-1210

1197

100.1

90.7

64.4

57.0

51.6

34.2

23.6

0.2521

0.8085

0.0001

1.2325

0.0114

0.0001

0.4164

1→15, 2→6

1→16, 2→7

1→17, 4→6, 3→7

1→21, 3→8

1→22, 4→8

1→23, 5→8

1→25, 2→8

1→28, 1→6

1→29, 1→7

1→31, 1→8

–16.516281055

202.2f

183.0

182.9

179.2

97.7

92.4

65.1

58.1

50.6

34.6

23.8

0.0001

0.0096

0.0094

0.0015

0.2411

0.2412

0.7927

0.0031

0.0013

1.1208

0.1646

0.0026

0.4392

1→7, 4→7, 3→7

1→9, 5→7

1→10, 5→7

1→11, 4→6, 3→7

1→12, 4→7, 3→6

1→15, 2→6

1→16, 2→7

1→17, 4→6, 3→7

1→21, 3→8

1→22, 4→8

1→23, 5→8

1→25, 2→8

1→28, 1→6

1→29, 1→7

1→31, 1→8

–16.500365172

206.7g

204.7

197.1

177.9

94.4

91.1

65.5

65.4

60.7

48.5

34.8

23.9

0.0217

0.0277

0.0055

0.0003

0.7174

0.2196

0.2234

0.0219

0.0052

1.0227

0.2690

0.0104

0.4354

1→7, 5→6

1→8, 5→7

1→10, 4→7, 3→6

1→11, 4→7, 3→6

1→12, 4→6, 3→7

1→15, 4→6, 3→7

1→16, 2→6

1→17, 2→7

1→21, 3→8

1→22, 4→8

1→23, 5→8

1→25, 2→8

1→28, 1→6

1→29, 1→7

1→31, 1→8

–16.520177428

(N2)2

(120)

180.4

169.6

109.3

109.2

106.8

106.7

106.5

106.3

105.1

105.0

100.1

99.5

91.6

89.4

79.0

77.4

65.1

57.1

56.8

0.0001

0.0011

0.0053

0.0744

0.0197

0.0424

0.0001

0.0010

0.0055

0.0005

0.0075

0.0025

0.2382

0.2310

0.2103

0.2436

0.6090

09337

0.0001

0.0010

0.0001

0.0018

0.0001

0.6428

1.8393

1→16; 10→11,8→12

1→23; 6→13

1→12; 9→12

1→29; 9→11

1→32; 10→11,5→11

1→33; 5→12

1→34; 10→14

1→36; 6→12

1→38; 6→11

1→39; 10→13,7→13,5→13

1→41; 8→13

1→48; 7→14

1→49; 7→13,5→13

1→52; 4→11 ,3→11

1→53; 4→12,3→12

1→54; 4→14

1→55; 4→13, 3→13

1→56; 8→12

1→57; 6→13,5→14

1→59; 4→12,3→12

1→61; 4→11 ,3→11

1→63; 4→13,3→13

1→65; 3→14

1→72; 10→15,7→15

1→76; 9→16

1→77; 7→15

183.5e

177.1

176.2

175.6

163.8

121.0

120.3

117.5

116.8

102.9

98.9

97.3

92.8

90.8

90.1

89.5

88.2

84.6

83.5

72.2

63.5

63.4

0.0001

0.0015

0.0002

0.0012

0.0532

0.0024

0.0097

0.0010

0.1790

0.1941

0.2436

0.2411

0.0193

0.0208

0.0072

0.3440

0.0520

0.4583

0.6163

0.0031

0.1413

0.0008

0.0009

0.0006

0.0074

1→14; 10→11,6→12,5,→11

1→16; 10→13

1→18; 7→12

1→19; 7→11

1→22; 6→11 ,5→12

1→28; 10→12

1→29, 10→11, 9→11

1→36; 9→12

1→37; 9→11

1→40; 5→13,4→13

1→41; 5→14,4→14

1→42; 3→11

1→43; 3→12

1→46; 7→13

1→47; 7→14

1→48; 6→13

1→54; 9→14,4→14

1→55; 5→13.4→13

1→56; 5→14

1→57; 5→12

1→60; 4→11

1→61; 4→12

1→64; 3→13

1→65; 3→14

1→72; 9→16

1→74; 10→15,5→15

J. Mazurkiewicz et al. / Natural Science 2 (2010) 1195-1210

1198

52.8

52.3

52.2

51.9

51.4

44.5

44.1

24.0

23.9

23.8

23.5

0.0029

0.0056

0.0041

0.0007

0.0008

0.0036

0.0002

0.0033

0.0315

0.3691

0.4317

1→80; 9→15

1→82; 5→15,3→15

1→83; 10→16,5→16

1→90; 7→16

1→92; 4→16

1→93; 5→15,3→15

1→95; 4→15,3→15

1→97; 4→16,3→16

1→116; 2→16

1→118; 1→15

1→120; 2→15

1→121; 1→16

–33.037415255

57.6

57.1

55.3

54.6

52.2

51.5

49.9

48.0

46.4

32.0

24.4

23.5

23.3

23.0

1.0470

1.2236

0.0614

0.0176

0.0004

0.0038

0.0017

0.0033

0.0021

0.0010

0.0007

0.3704

0.3637

0.0030

1→76; 10→16,7→15

1→77; 10→16,7→15

1→79; 19→15,9→15

1→83; 9→15

1→86; 5→16,4→16

1→87; 3→15

1→89; 7→16

1→93, 5→16,4→16

1→95; 4→15

1→109; 2→12

1→116; 2→15

1→118; 2→16

1→119; 1→15

1→121; 1→16

–33.125361948

(N2)5h

(750)

107.8

107.5

105.8

105.7

100.2

99.7

98.2

97.9

97.7

97.6

97.5

97.0

96.8

96.4

96.3

96.2

96.1

95.3

95.1

90.4

89.4

88.7

88.1

87.8

57.7

57.5

57.2

57.1

23.6

23.5

23.4

23.3

0.0855

0.0755

0.1090

0.0561

0.0573

0.0773

0.1304

0.1615

0.0550

0.0764

0.0697

0.0700

0.1010

0.1767

0.0520

0.0707

0.0575

0.1212

0.0629

0.0534

0.5087

0.7134

0.5659

0.8357

0.8161

0.2806

1.8171

0.7356

1.4507

1.6333

0.2989

0.3817

0.2869

0.3947

0.4136

1→122; none

1→126; 12→29

1→157; none

1→159, none

1→232; none

1→238; 13→32

1→259; 8→26

1→261; 8→27

1→268; 12→33

1→270; none

1→273; none

1→276; none

1→279; 13→31

1→280; none

1→281; 13→30

1→282; none

1→283; 10→35

1→284; 10→33

1→296; none

1→298; none

1→317; none

1→318; none

1→319; none

1→320; none

1→321; none

1→427; 24→37

1→428; 25→38

1→429; none

1→430; 21→39

1→431; 23→36

1→731; 5→36

1→738; 4→37

1→745; 3→38

1→748; 2→39,1→39

1→749; 2→40,1→40

–82.746665858

104.4e

104.3

104.1

104.0

103.6

103.5

102.7

102.0

101.5

100.0

99.9

97.1

96.9

96.4

96.2

95.9

95.1

94.6

91.6

91.4

90.8

90.6

90.4

90.3

89.9

89.6

89.3

89.2

88.8

57.6

57.4

57.3

57.2

57.1

57.0

56.9

55.8

23.7

23.6

23.5

23.4

0.1559

0.0878

0.1225

0.0821

0.1348

0.1039

0.0575

0.0686

0.1344

0.0704

0.0817

0.1319

0.2495

0.1514

0.1524

0.0574

0.1476

0.1180

0.0688

0.0564

0.0649

0.7556

0.0562

0.3470

0.2270

0.0968

0.0718

0.7598

0.0588

0.0992

0.3172

0.5672

0.5401

0.0624

0.5997

2.9915

0.0504

1.1596

0.1159

0.2865

0.1408

0.4665

0.2956

0.2579

0.5530

0.3665

1→187; 11→28,11→29

1→188; 11→28,11→29

1→189; none

1→190; none

1→191; 22→34,10→34

1→192; 22→35,10→35

1→196; 19→33

1→200; 13→28,8→31

1→202; 16→30,8→30

1→205; 22→34

1→206; 22→35

1→217; 16→31

1→219; 6→27

1→220; 6→26

1→226; 17→33,9→33

1→235; none

1→235; 7→28,7→29

1→237; 7→28,7→29

1→241; 20→35

1→244; 14→31

1→247; 19→35

1→261; none

1→266; 15→33,12→31

1→272; none

1→273; none

1→275; 14→32,14→33

1→277; none

1→279; none

1→282; 11→30

1→284; 10→26

1→286; 10→26

1→289; none

1→431; 22→39,19→38

1→432; 25→37,22→37

1→434; 16→37

1→435; none

1→437; 23→36

1→438; 25→40

1→439; 22→36

1→441; 22→36,13→36

1→453; 24→38,23→38

1→727; 5→40

1→730; 1→36

1→733; 3→38

1→734; 2→37

1→735; 4→39

–82.654318825

aValues of E [nm] given in italics denote novel transitions generated on the application of electric field. Values in bold italics denote transitions

which will cease on application of more intensive electric field; bThe oscillator strength;cIn the field of 0.001 a.u; dIn the field of 0.005 a.u;eIn

the field of 0.01 a.u; fIn the field of 0.05 a.u; gIn the field of 0.10 a.u; hThere were 285 and 291 active transitions in the spectra without and with

the 0.01 a.u. electric field, respectively. In this Table only transitions with f >0.0500 are quoted.

of nitrogen provided UV spectrum composed of 5 bands

in the range of 100.2 to 23.6 nm, although the computa-

tions considered totally 30 transitions. Majority of those

transitions appeared inactive i. e. their oscillator strength,

J. Mazurkiewicz et al. / Natural Science 2 (2010) 1195-1210

1199

f = 0.0000. The most intensive transition was located at

56.9 nm. Application of the electric field of 0.001 a.u.

only slightly modifies the original spectrum. There is an

increase in the number of active transitions by one ex-

tremely weak transition at 51.7 nm and the 1→17 transi-

tion at 57.0 nm changed its HOMO →LUMO character-

istics. Application of the electric field of such energy

stabilizes the molecule by 0.016582114 a.u. The 0.005

a.u. electric field increases the number of the active tran-

sitions to 10. All four extremely weak transitions appear

on the red side of the spectrum around 175 nm. The

bands shifts are almost negligible. The longwavelength

transitions move slightly red whereas the shortwave-

length transitions slightly migrate towards blue. Intensi-

ties of the transitions increase. The field of such energy

destabilizes the molecule in respect to that under the

influence of the weaker field. The destabilization energy

is only 0.013825361 a.u but nevertheless this system is

still more stable than that without the influence of the

electric field. Further increase in the energy of applied

electric field to 0.01 a.u. produces this time additional

transitions in the central (transitions 1→21 and 1→22 at

64.4 nm) and in shortwavelength region of the spec-

trum (1→28 and 1→29 transitions at 34.2 nm). Thus,

the total number of active transitions rises to 14. Addi-

tionally, two the longest wavelength transitions changed

their HOMO→LUMO structure. The electric field of

such energy consequently produces further destabiliza-

tion of the nitrogen molecule by 0.014970233 a.u but

even now the molecule still remains more stable than

without the influence of the field. Just the application of

the 0.05 a.u. field which destabilizes the molecule by

0.0308861116 a.u. reduces the stability of that molecule

below that it had without the influence of the electric

field. That field adds further longest wavelength transi-

tion at 202.2 nm causing additionally slight bathochro-

mic shifts of the transitions on both red and blue sides of

the spectrum and some bands in the central region of the

spectrum move slightly hypsochromically. The electric

field of 0.1 a.u. introduces more pronounced changes in

the spectrum. The 1→9 transition ceases and the 1→8

transition appears instead. Some transitions change their

HOMO-LUMO structure. The 0.1 a.u. electric field in-

creases the molecule stability over that noted without

field by 0.011073860 a.u. Thus, the stabilization of the

molecule by electric field is non-linear in the energy of

that field.

The simulations of the spectrum for the system of two

nitrogen molecules provides the spectrum considerably

enriched in the transitions. In the spectrum for the sys-

tem without any influence of the external electric field

the number of transitions increases from totally 30 and 5

among them active for single nitrogen molecule to to-

tally 120 and 38 active, respectively. In this spectrum, all

excitations specific for the spectrum of the single nitro-

gen molecule cannot be recognized. The 1→52, 1→53,

1→57, 1→77 and 1→121 transitions resembling these in

the spectrum of the single nitrogen molecule in their

position and intensity have more complex structure. In

this spectrum, two longest wavelength transitions are

less intensive than relevant transitions in the spectrum of

the single molecule but three shorter wavelength transi-

tions are more intensive than the corresponding transi-

tions in the spectrum of the single molecule. In the sys-

tem of two nitrogen molecules the total energy of the

system is lower than doubled energy of the single nitro-

gen molecule. The energy of stabilization due to inter-

molecular interactions of two nitrogen molecules is

0.008076807 a.u. The system of five nitrogen molecules

provides stabilization energy of 0.173319988 a.u. Thus,

the electric field providing stabilization of the system

increases with the number of interacting molecules.

In the bimolecular nitrogen system under the influ-

ence of the 0.01 a.u. electric field also the stabilization

resulting from the intermolecular interactions is noted.

This stabilization by 0.082799838 a.u. is stronger than in

corresponding monomolecular system However, in the

pentamolecular nitrogen system under the influence of

the same electric field the stabilization energy is lower

and reaches 0.072913550 a.u. Thus, in contrast to elec-

tric field non-perturbed systems an increase in the num-

ber of interacting molecules of nitrogen decreases the

energy of stabilization.

Figure 1 presents mapping of isosurface of the nitro-

gen molecule prior (left) and after (right) exposure to the

electric field of 0.01 a.u. In electric field perturbed

molecule a negative charge concentrates on both nitro-

gen atom increasing from 0.000 in non-perturbed mole-

cule to -0.048 in the molecule in the electric field.

Figure 2 presents optimized natural and 0.01 a.u.

electric field induced orientation of two and five nitro-

gen molecules.

Two nitrogen molecules without any influence of the

electric field remain practically nonpolarized and are

fairly arbitrarily mutually oriented. Under the influence

of the electric field they turn polarized and their bipolar

character induces certain charge density dependent mu-

tual orientation. Under the absence of the external elec-

tric field, very slightly polarized five nitrogen molecules

form practically disordered system whereas the electric

field polarized the molecules and the polarization for

particular molecules is different from one another as the

effect of their own field. Mutual orientation of these

molecules is clearly controlled by charge density inter-

actions.

The oxygen molecule considered as biradical provides

J. Mazurkiewicz et al. / Natural Science 2 (2010) 1195-1210

1200

Figure 1. Mapping of isosurface of the nitrogen molecule prior (left) and after (right) exposure to the

electric field of 0.01 a.u.

a b

c d

Figure 2. Optimized mutual orientation of two and five nitrogen molecules without field (a and c) and under the influ-

ence of the 0.01 au. electric field (b and d).

the spectrum composed of 8 transitions residing between

131.1 and 20.1 nm although there were considered 22

transitions (Table 2).

Its total energy is almost twice as low as that of the

nitrogen molecule. Exposure of the molecule to the elec-

tric field influences the total energy of the molecule in

an alternant way. A weak 0.001 a.u. electric field in-

creases the total energy of the molecule by 0.018720379

a.u. what means that the molecule becomes more oxida-

tive. Increase in the energy of the applied electric field to

0.005 a.u. stabilizes the former system by 0.025063273

a.u. in respect to the total energy of the initial and ex-

posed to the 0.001 a.u. energy molecules. The exposure

of the molecule to 0.01, 0.05 and 0.1 a.u. electric field

accordingly increases the total energy of the molecule by

0.046010234, decreases it by 0.047923038 and increases

again by 0.012487111 a.u., respectively. On exposure to

the 0.001 a.u. field, the number of the transitions in-

creases by one (1→5) appearing on the red side of the

spectrum at 136.6 nm. A slight bathochromic shift of the

other bands is observed with the decrease in the intensity

of the longwavelength and increase in the intensity of

the shortwavelength transitions. At the 0.005 a.u. field

two additional bands on the shortwavelength side of the

spectrum (1→18 and 1→19) are added. Simultaneously,

the 1→23 transition vanishes. This time, a slight hyp-

sochromic shift of all the bands takes place and their

intensities increase and decrease in the longwavelenght

and short wavelength regions, respectively. Further in-

crease in the energy of the applied electric field to 0.01

a.u. produces two additional transitions appearing in the

longwavelength (1→6) and central (1→14) region of the

spectrum. The “native” transitions practically stay in

place and their intensities change subtly. The increase in

the energy of applied field to 0.05 a.u. generates four

novel transitions in the central region (1→12, 1→13,

1→15 and 1→16) and, additionally, two transitions in

the shortwavelength region (1→20 and 1→21) of the

J. Mazurkiewicz et al. / Natural Science 2 (2010) 1195-1210

1201

Table 2. Simulated electronic spectra of one, two and five oxygen molecules without exposure and with exposure to external

electric field.

Transition energy (E) [nm] and its characteristicsa

Without electric field With electric field

Molecule

(total number

of transitions) E fb

Orbital → orbital;

HOMO → LUMO

and total energy [a.u.]

E fb

Orbital → orbital;

HOMO → LUMO

and total energy [a.u.]

131.1

88.0

80.3

46.1

23.3

20.1

0.3559

0.0504

0.0926

0.8969

0.0057

0.2837

1→7

1→8

1→9

1→10

1→11

1→17

1→22

1→23

–23.930508098

136.6c

135.4

88.2

80.7

46.2

23.5

20.3

0.0010

0.3525

0.0490

0.0936

0.9227

0.0060

0.2925

1→5

1→7

1→8

1→9

1→10

1→11

1→17

1→22

1→23

–23.911787719

136.0d

132.40

87.9

80.2

46.1

43.0

39.1

23.2

20.1

0.0031

0.3535

0.0507

0.0924

0.8888

0.0001

0.0056

0.2810

1→5

1→7

1→8

1→9

1→10

1→11

1→17

1→18

1→19

1→22

1→23

–23.936250992

136.1e

136.0

132.1

87.9

80.2

53.5

46.1

42.9

39.1

23.2

20.1

0.0068

0.0002

0.3499

0.0502

0.0501

0.0927

0.0001

0.8839

0.0018

0.0007

0.0056

0.2801

1→5

1→6

1→7

1→8

1→9

1→10

1→11

1→14

1→17

1→18

1→19

1→22

1→23

–23.890240758

141.1f

141.1

126.8

85.0

78.9

59.7

52.8

52.7

46.5

42.0

38.7

29.8

23.0

0.0088

0.0079

0.3445

0.0213

0.0212

0.1124

0.1123

0.0005

0.0004

0.0006

0.0005

0.0012

0.7697

0.0411

0.0341

0.0023

0.0051

1→5

1→6

1→7

1→8

1→9

1→10

1→11

1→12

1→13

1→14

1→15

1→16

1→17

1→18

1→19

1→20

1→21

1→22

–23.938163796

O2

(22)

157.2g

157.0

127.8

83.7

74.4

0.0196

0.0191

0.2882

0.0036

0.1116

1→5

1→6

1→7

1→8

1→9

1→10

J. Mazurkiewicz et al. / Natural Science 2 (2010) 1195-1210

1202

74.4

61.9

56.0

54.8

48.3

41.2

38.1

30.7

23.8

20.5

0.0015

0.0019

0.00100.

0086

0.0026

0.0022

0.7561

0.0565

0.1100

0.0096

0.0064

0.2826

1→11

1→12

1→13

1→14

1→15

1→16

1→17

1→18

1→19

1→20

1→21

1→22

1→23

–23.925676685

(O2)2

(94)

147.1

85.6

81.0

0.2070

0.1178

0.0264

1→12

1→22

1→25

–47.926248950

151.3g

135.5

85.8

81.4

0.2056

0.0001

0.1182

0.0255

1→10

1→12

1→24

1→27

–47.906263740

(O2)5

(598)

203.8

179.5

169.6

161.8

157.5

153.6

152.5

147.4

137.9

135.5

134 2

129.9

88.1

87.7

85.8

85.7

85.6

81.6

71.6

59.2

56.8

47.6

29.9

0.0001

0.0007

0.0012

0.0003

0.0354

0.0006

0.1145

0.0501

0.0001

0.0008

0.0013

0.0001

0.0004

0.0003

0.0005

0.1161

0.0251

0.0002

0.0004

0.0003

0.0001

0.0007

1→27

1→38

1→40

1→43

1→49

1→50

1→52

1→59

1→67

1→70

1→72

1→77

1→122

1→125

1→132

1→133

1→134

1→152

1→193

1→240

1→255

1→350

1→491

–119.316786473

286.9g

286.8

286.1

241.6

165.2

161.9

156.4

142.1

131.5

104.9

101.3

97.4

97.3

46.1

45.2

41.5

40.8

38.9

37.6

37.5

37.3

32.4

32.0

31.3

29.6

23.4

0.0088

0.0089

0.0004

0.0002

0.0018

0.0008

0.0023

0.0005

0.0026

0.0005

0.0022

0.0021

0.0001

0.0694

0.00010.

0009

0.4430

0.0017

0.0002

0.0001

0.0005

0.0004

0.00040.

0055

0.0001

0.0002

0.0001

1→2

1→3

1→4

1→6

1→11

1→13

1→16

1→20

1→21

1→27

1→32

1→38

1→39

1→83

1→84

1→96

1→97

1→99

1→107

1→120

1→121

1→122

1→145

1→146

1→148

1→149

1→161

1→247

–102.846760782

aThe data in the Table presented in italics relate to the novel transitions generated by the application of an electric field of a given energy. Such

values in bold italics denote transitions which cease on application of the electric field of the next higher energy; bThe oscillator strength; cIn

the field of 0.001 a.u.; dIn the field of 0.005 a.u; eIn the field of 0.01 a.u.fIn the field of 0.05 a.u; gIn the field of 0.10 a.u.

spectrum. The longest wavelength transitions shift ba-

thochromically whereas the other transitions move op-

-posite direction. At the 0.1 a.u. field only one novel

band appears as the shortest wavelength 1→23 transition.

All transitions except 1→18 and 1→19 move batho-

chromically. Simultaneously, longwavelength bands de-

crease their intensities whereas the transitions in the

shortwavelength and central regions increase their inten-

sities. Except the 1→18 transition, the other transitions

increase their intensities.

Such lack of relationships between applied electric

field and changes in the spectra pattern could result from

a complex response from lone electron pairs and un-

paired spins of both oxygen atoms to the varying dipole

moment forced by applied electric field.

Figure 3 presents mapping of isosurface of the oxy-

gen molecule without and with electric field of 0.01 a.u.

In the system of two oxygen molecules there is a sta-

bilization due to the intermolecular interactions. The

total energy of the system is lower by 0.063232754 a.u.

than doubled total energy of the single molecule. The

0.01 a.u. field cooperates with these interactions and the

stabilization of the system reaches 0.125782224 a.u. In

the system of five oxygen molecules intermolecular in-

teractions are less efficient. The total energy of the sys-

tem is higher by 0.336754017 a.u. than five-fold energy

J. Mazurkiewicz et al. / Natural Science 2 (2010) 1195-1210

1203

Figure 3. Mapping of isosurface of the oxygen molecule without electric field (left) and at 0.01 a.u.

electric field (right).

of the single molecule. The 0.1 a.u. electric field intro-

duces dramatic destabilization of the system. The cor-

res-ponding energy of destabilization is -16.604443008

a.u pointing to a highly oxidative ability of such system.

The field-perturbed oxygen molecules are clearly po-

lar and, therefore, they form the charge density regulated

system. In the system of five molecules their polariza-

tion entirely ceases and their orientation is rather arbi-

trary. The application of the electric field recovers the

polarization of the molecules which influences certain

mutual orientation of those molecules.

Figure 4. presents optimized orientation of two and

five oxygen molecules without intervention of electric

field and in the 0.01 a.u. electric field.

The simulation provided the UV spectrum of a single

water molecule consisting of 7 transitions, all with f >>

0.0000 (Table 3). Nine other transitions are inactive (f =

0.0000).

Application of the electric field of 0.01 a.u. modifies

the spectral pattern of unperturbed molecule on the red

side. Novel transitions appear at 100.1 and 91.8 nm and

one transition in original, unperturbed spectrum located

at 90.9 nm ceases. The transitions shift slightly towards

blue and their intensities vary irregularly.

Figure 5 presents the mapping of the isosurface of in-

dividual water molecules without and with the influence

of electric field of 0.01 a.u.

The electric field concentrates the negative charge on

the oxygen atom. The negative charge declines from

-0.383 to -0.414 and, in the same time, the positive

charge increased from 0.191 to 0.207. Thus, water

molecule becomes more acidic and more prone to form

dimers, trimers and so on. Such behavior can be respon-

sible for several peculiar, poorly understood properties

of water [27]. This result can be responsible for stabili-

zation of the molecule in the 0.01 a.u. field by

0.019448846 a.u.

In the spectrum of the system of 5 water molecules

totally 400 transitions in the UV region are considered

and among them only 199 transitions are characterized

by f > 0.0000. (Table 3). The transitions are situated in

the region from 111.3 to 27 nm. The five fold increase of

(a) (b)

(c) (d)

Figure 4. Optimized orientation of two and five oxygen molecules without intervention of electric field (a and c)

and in the 0.01 a.u. electric field (b and d).

J. Mazurkiewicz et al. / Natural Science 2 (2010) 1195-1210

1204

Figure 5. Mapping of isosurface of the water molecule prior (left) and after (right) expo-

sure to the electric field of 0.01 a.u.

Table 3. Simulated electronic spectra of one and five water molecules without exposure and with exposure to 0.01 a.u. external

electric field.

Transition energy (E) [nm] and its characteristicsa

Without electric field With electric field

Molecule

(total number

of transitions) E fb

Orbital → orbital

HOMO → LUMO

and total energy [a.u.]

E fb

Orbital → orbital

HOMO → LUMO

and total energy [a.u.]

H2O

(16)

111.3

90.9

84.3

64.5

56.1

29.6

29.0

0.0329

0.0106

0.1866

0.2536

0.3382

0.0909

0.1760

1→3; 4→5

1→8; 3→5

1→9; 3→6

1→12; 2→5

1→13; 2→6

1→16; 1→5

1→17; 1→6

–13.581465020

110.9

100.1

91.8

83.0

62.9

54.4

29.8

28.7

0.0317

0.0034

0.0140

0.1729

0.2860

0.2969

0.0787

0.1817

1→3; 4→5

1→6; 4→6

1→7; 3→5

1→9; 3→6

1→12; 2→5

1→13; 2→6

1→16; 1→5

1→17; 1→6

–13.600913866

(H2O)5c

(400)

91.3

85.7

84.9

84.4

84.1

83.9

83.1

66.2

65.1

63.8

63.4

62.8

58.4

58.1

57.3

57.1

56.3

55.8

54.9

54.6

54.3

30.1

30.0

29.7

29.6

29.5

29.0

28.8

0.0574

0.1692

0.1205

0.2383

0.0951

0.1172

0.0607

0.1003

0.1030

0.2198

0.0922

0.1638

0.2308

0.0934

0.1485

0.1396

0.0900

0.4467

0.0622

0.0796

0.0880

0.0519

0.0936

0.1125

0.1123

0.0685

0.1576

0.1042

0.1683

0.0947

1→33; none

1→37; 13→26,11→26

1→40; 15→30

1→43; 13→27,11→27

1→45; 19→21

1→46; 12→28

1→50; none

1→51; 16→21

1→181; 10→21

1→191; 9→22

1→199; none

1→204; 13→29

1→208; 8→23

1→219; 10→22,10→26

1→221; 10→22,10→26

1→226; 9→27,7→21

1→228; 7→21

1→233; 10→28

1→238; 10→29

1→247; 8→25

1→250; none

1→255; 6→24

1→313; 4→21, 4→23

1→314; 5→22

1→316; 5→26

1→317; none

1→319; 5→27

1→329; 3→28

1→331; 4→24

1→336; none

–67.963599996

110.6

94.5

87.4

86.8

86.6

85.6

84.7

81.8

68.3

65.8

64.6

62.3

62.1

61.8

55.8

55.7

55.4

55.2

54.6

54.2

53.8

30.3

29.9

29.6

28.4

27.8

27.3

0.0510

0.0800

0.1169

0.0950

0.0765

0.1341

0.1493

0.0939

0.0540

0.0775

0.0545

0.1045

0.5283

0.2575

0.5738

0.0652

0.0967

0.0909

0.0635

0.0721

0.0558

0.1820

0.0584

0.0767

0.1206

0.0849

0.1848

0.0722

0.0681

0.0518

1→9; none

1→29; none

1→43; 20→28

1→46; 18→21

1→47; 17→29

1→50; 14→26,13→26

1→52; 17→30

1→59; 11→27

1→156; 12→25

1→172; none

1→179; none

1→198; 11→22,11→23

1→199; 6→21

1→202; 7→23,7→24

1→231, 7→27

1→233; 10→29

1→234; 8→24

1→234; 10→26

1→239; 10→28

1→246; 11→30,10→30

1→252; none

1→254; 6→26

1→319; 4→21,4→22

1→323; 5→29

1→327; 5→26

1→328; 4→24,4→25

1→329; 5→30

1→350; 5→26,3→26

1→358; 3→27,2→27

1→368; 3→27,2→27

–68.055033213

the water molecules makes the system more stable by

0.056274896 a.u. The electric field of. 0.01 a.u. reduces

the number of active transitions with f > 0.0000 from

217 to 214. Applied field makes the structure of particu-

J. Mazurkiewicz et al. / Natural Science 2 (2010) 1195-1210

1205

lar transitions entirely different from these in the

field-unperturbed spectrum. Application of the 0.01 a,.u.

field stabilizes the system of five water molecules in

respect to that without influence of the field. The stabi-

lization energy reaches relatively high value of

1.091433217 a.u. The stabilization can result from the

facilitation of the formation of intermolecular hydrogen

bonds.

The simulated UV spectrum of carbon dioxide con-

sists of totally 64 transitions among whose 26 are active

(f > 0.0000) (Table 4).

Based on the comparison of the wavelengths and in-

tensities of computed transitions, the application of the

0.01 a.u. field eliminates from the spectrum of unper-

turbed molecule weak transition at 222.1, changes the

structure of the 1→14 transition and adds another weak

transitions 1→17, 1→20, 1→44 and 1→55. Comparable

transitions in unperturbed and field-perturbed spectra

shift irregularly towards blue and red and also their in-

tensities vary irregularly. Applied 0.01 a.u. field destabi-

lized the molecule by 0.018192592 a.u.

Figure 6 presents changes of the electron density in

the carbon dioxide molecule prior to and after applica-

tion of the field of 0.01 a.u.

That Figure shows that after application of the electric

field of 0.01 a.u. negative charge non-equivalently con-

centrates on the oxygen atoms whereas positive charge

on the carbon atom changes negligibly. The destabiliza-

tion can result from the effect of the field upon interac-

tions with involvement of induced dipoles. Simulation of

the system of two CO2 molecules analyzed totally 256

transitions among which 86 are active with f > 0.0000.

The bimolecular system of CO2 is less stable by

0.007099722 a.u. Likely this destabilization results from

repulsion of the molecules. The 0.01 a.u. field increases

the repulsion.

The spectrum of the CO2 – H2O system illustrates the

state of the well known equilibrium between carbonic

acid and its components. As indicated by the total energy

of the systems, the 0.01 a.u. field causes destabilization

increasing total energy by 0.015102407 a.u. That field

entirely changes the spectrum. Except the shortest

wavelength 1→145 transition, corresponding transitions

which can be recognized in both spectra have different

HOMO-LUMO characteristics (Table 4).

The simulation of the UVVIS spectrum of the unper-

turbed and field perturbed ammonia molecule provids

totally 24 transitions among whose only 12 transitions in

both cases are active (Table 5).

This difference appears in the structure of the transi-

Table 4. Simulated electronic spectra of one and two carbon dioxide molecules as well as carbon dioxide – water 1:1 system with-

out exposure and with exposure to 0.01 a.u. external electric field.

Transition energy (E) [nm] and its characteristicsa

Without electric field With electric

field

Molecule

(total number

of transi-

tions) E fb

Orbital → orbital

HOMO → LUMO

and total energy [a.u.]

E fb

Orbital → orbital

HOMO → LUMO

and total energy [a.u.]

CO2

(64)

222.1

142.2

138.3

131.8

131.6

130.8

120.3

101.3

97.7

94.9

91.8

91.5

77.2

69.5

61.8

61.7

52.2

48.4

45.6

35.2

33.3

33.2

30.3

29.2

23.8

23.3

0.0004

0.3564

0.0001

0.0014

0.0013

0.2958

0.2605

0.0362

0.1308

0.1582

0.0609

0.0110

1.3488

0.0012

0.0610

0.0618

0.0008

0.0062

0.1242

0.0021

0.0368

0.0406

0.2102

0.0022

0.0060

0.3157

1→7; 8→9,7→10

1→14; 8→9,8→11,7→10

1→15; 6→9,5→10

1→18; 6→10,5→9

1→19; 6→9,5→10

1→21; 8→11 ,4→9

1→24; 4→9

1→29; 3→9

1→30; 3→10

1→31; 3→9

1→33; 6→11

1→34; 5→11

1→36; 4→11

1→37; 3→11

1→40; 8→12

1→41; 7→12

1→45; 5→12

1→47; 4→12

1→49; 3→12

1→52; 2→9

1→57; 1→9

1→58; 1→10

1→60; 2→11

1→61; 1→11

1→64; 2→12

1→65; 1→12

140.8

138.8

133.1

132.7

122.3

121.9

99.7

97.9

96.3

93.4

77.5

69.8

61.9

61.8

52.5

52.4

48.4

45.6

35.2

33.4

30.4

29.5

0.1730

0.0001

0.6290

0.0059

0.0091

0.0032

0.0705

0.0325

0.1030

0.0906

0.0743

0.0858

1.3979

0.0092

0.0605

0.0606

0.0002

0.0003

0.0085

0.1209

0.0007

0.0002

0.0397

0.0406

0.2180

0.0030

1→14; 8→11

1→17; 7→11

1→18; 8→9, 8→11,7→10

1→19; 6→10,5→9

1→20; 6→9

1→23; 4→10

1→24; 4→9

1→29; 3→9

1→30; 3→10

1→31; 3→9

1→33; 6→11

1→34; 5→11

1→36; 4→11

1→37; 3→11

1→40; 8→12

1→41; 7→12

1→44; 6→12

1→45; 5→12

1→47; 4→12

1→49; 3→12

1→53; 2→9

1→55; 2→10

1→57; 1→9

1→58; 1→10

1→60; 2→11

1→61; 1→11

J. Mazurkiewicz et al. / Natural Science 2 (2010) 1195-1210

1206

–29.238512694 23.8

23.4

0.0006

0.3206

1→64; 2→12

1→65; 1→12

–29.220320102

(CO2)2c

(256)

134.6

133.9

132.9

98.5

98.3

98.0

96.4

93.0

92.9

92.8

92.6

77.6

77.5

61.7

45.6

33.3

30.4

23.4

0.0688

0.6023

0.9910

0.0585

0.0924

0.1127

0.1165

0.0520

0.0723

0.0772

0.0611

0.0659

2.5980

0.1587

0.1185

0.0574

0.0661

0.1312

0.1142

0.0772

0.0755

0.4096

0,5414

1→34; 16→17

1→35; 16→20

1→38; 13→17

1→72; 6→20

1→73; 5→17

1→74; 5→18

1→75; 6→19

1→82; 16→22,13→22

1→88; 10→21

1→89; 11→22

1→90; 12→21,9→21

1→91; 12→22,9→22

1→118; 8→22,7→21

1→119; 8→22

1→150; 16→23,13→24

1→152; 15→24

1→153; 14→23

1→176; 5→23

1→177; 6→24

1→209; 2→18,1→18

1→211; 2→20,1→17

1→230; 4→21,3→22

1→248; 2→23,1→24

–58.470925666

140.9

140.6

134.1

132.6

121.9

98.1

97.6

95.8

94.0

93.9

93.0

77.6

77.5

61.9

61.8

45.5

30.5

30.4

23.5

23.4

0.2113

0.0587

0.8054

0.5640

0.0994

0.0870

0.1054

0.1055

0.1002

0.1033

0.0832

1.6660

1.1105

0.0603

0.0610

0.06910

.0603

0.1249

0 .1115

0.2172

0.2118

0.3406

0.2747

1→34; 14→21

1→35; 16→22

1→42; 16→19,15→20

1→45; 14→17,14→21,13→18

1→55; 7→17

1→86; 6→20

1→87; 5→18

1→93; 3→17

1→96; 12→22;11→22,6→19

1→97; 12→22,11→22,6→20

1→99; 9→21

1→126; 10→22

1→127; 7→21

1→148; 16→24

1→149; 15→24

1→150; 14→23

1→151; 13→23

1→182; 6→24

1→183; 5→23

1→226; 4→22

1→227; 2→21

1→250; 3→24

1→251; 1→23

–58.434944686

CO2+H2O

(144)

138.8

132.9

96.4

95.8

92.6

92.4

91.0

86.6

84.3

76.7

65.6

63.1

61.7

56.9

55.5

45.2

30.1

29.3

28.8

23.3

0.0772

0.7053

0.0840

0.0772

0.1133

0.0866

0.0901

0.1552

0.1701

1.1481

0.0577

01478

0.0511

0.0858

0.0663

0.2342

0.0938

0.1839

0.0502

0.1674

0.3009

1→14; 12→13,10→15

1→24; 11→14,10→13

1→46; 4→14

1→47; 4→13

1→49; 8→15,7→15

1→50; 8→15,7→15

1→51; 9→15,9→16

1→53; 9→15,9→16

1→54; 9→17

1→64; 6→15

1→72; 5→15

1→76; 5→15,5→16

1→77; 11→18,10→18

1→78; 11→18,10→18

1→85; 8→17

1→91; 5→17

1→107; 4→18

1→128; 2→15

1→129; 3→16

1→131; 3→17

1→145; 1→18

–42.851775857

138.6

129.9

121.5

100.7

99.1

89.8

84.2

78.4

74.0

65.4

61.3

56.8

46.1

30.1

29.5

29.4

23.1

0.3129

0.0001

0.2548

0.0623

0.0971

0.0798

0.1528

1.1594

0.1325

0.2515

0.0632

0.0629

0.3200

0.0782

0.2431

0.0606

0.0950

0.2562

1→14; 12→15,11→14

1→21; 12→15

1→25; 6→13

1→36; 9→13,5→13

1→50; 9→14,5→14

1→53; 8→15,7→15,5→14

1→55; 9→17

1→62; 9→15,6→15

1→64; 9→15,6→15

1→78; 4→16

1→87; 12→18

1→88; 11→18

1→93; 4→17

1→105; 9→18,5→18

1→127; 3→16,2→15

1→128; 3→15,3→17,2→15

1→129; 3→17

1→145; 1→18

–42.836673450

aThe data in the Table presented in italics relate to the novel transitions generated by the application of an electric field of a given energy. Such val-

ues in bold italics denote transitions which cease on application of the electric field of the next higher energy; bThe oscillator strength; cIn this Table

only transitions of f ≥0.0500 are given. The total number of the transitions with; f > 0.0000 is 86 and 82 in the spectra of one and two carbon diox-

ide without and with electric field, respectively. In the carbon dioxide – water system the relevant numbers are 67 and 68, respectively. Values of E

[nm] given in italics denote novel transitions generated on the application of electric field. Values in bold italics denote transitions which will cease

on application of more intensive electric field.

Table 5. Simulated electronic spectra of single molecule of ammonia without exposure and with exposure to 0.01 a.u. external

electric field and analogous computations for the ammonia-water system.

Transition energy (E) [nm] and its characteristics

Without electric field With electric field

Molecule

(total number

of transitions) E fa

Orbital → orbital

HOMO → LUMO

and total energy [a.u.]

E fa

Orbital → orbital

HOMO → LUMO

and total energy [a.u.]

NH3

(24)

123.3

111.7

106.0

71.2

0.0270

0.0532

0.0643

0.0112

1→3; 4→5

1→6; 4→6

1→7; 4→7

1→11; 3→5

120.9

109.9

105.9

71.2

0.0191

0.0682

0.0738

0.0189

1→3; 4→5

1→6; 4→6

1→7; 4→7

1→11; 3→5

J. Mazurkiewicz et al. / Natural Science 2 (2010) 1195-1210

1207

67.6

65.9

62.9

62.0

54.5

32.5

31.6

31.1

0.0050

0.0107

0.4495

0.4795

0.1984

0.0196

0.1124

0.1380

1→14; 2→5

1→15; 3→7,2→6

1→17; 3→6,2→7

1→18; 3→7,2→6

1→19; 3→6,2→7

1→23; 1→5

1→24; 1→6

1→25; 1→7

–10.944414844

69.7

67.5

63.9

63.5

55.7

32.8

32.1

31.7

0.0030

0.0012

0.4548

0.4811

0.2366

0.0278

0.1187

0.1347

1→14; 2→5

1→15; 3→7,2→6

1→17, 3→6,3→7,2→6

1→18; 3→6,2→6

1→19; 3→2,2→7

1→23; 1→5

1→24; 1→6

1→25; 1→7

–10.905433106

NH3 + H2O

(80)

128.3

110.8

109.6

109.3

103.1

89.6

88.8

83.5

83.3

80.3

73.7

71.7

69.5

69.0

66.9

64.4

64.3

63.7

62.0

60.1

59.9

58.2

57.4

56.3

56.1

54.3

53.5

52.5

51.6

50.4

33.1

31.4

31.2

31.0

30.0

29.2

28.6

27.1

26.8

0.0520

0.0300

0.0342

0.0019

0.0149

0.0026

0.1751

0.0094

0.0034

0.0061

0.0082

0.0025

0.0108

0.0268

0.1634

0.0589

0.0410

0.0178

0.4280

0.5103

0.0107

0.0024

0.3176

0.0012

0.0241

0.1057

0.0002

0.0044

0.0011

0.0069

0.1313

0.1521

0.0003

0.0150

0.0866

0.0164

0.1480

0.0019

0.0003

1→3; 8→9

1→7; 8→12

1→8; 7→10

1→9; 8→13

1→11; 7→11

1→14; 8→10,6→10

1→16; 8→10,6→10

1→18; 6→11

1→19; 7→9

1→21; 8→11

1→25; 6→9

1→28; 7→12

1→31; 7→13

1→33; 5→9

1→34; 4→9

1→37; 6→12,3→10

1→38; 6→12,3→10

1→40; 6→13,5→13,4→12

1→42; 6→13,4→12

1→44; 5→12,4→13

1→45; 5→13,4→12

1→47; 5→10

1→49; 3→9

1→50; 5→11,3→11

1→52; 4→10

1→54; 5→11 ,3→11

1→55; 5→12,4→13

1→57; 4→11

1→59; 3→12

1→61; 3→13

1→65; 2→9

1→67; 2→12

1→69; 2→13

1→70; 2→10

1→72; 2→11

1→74; 1→10

1→76; 1→9

1→77; 1→11

1→79; 1→12

1→81; 1→13

–24.567018796

115.7

108.9

107.4

102.4

95.4

89.0

84.8

78.5

75.6

73.6

70.9

69.2

68.3

67.8

66.8

66.2

65.0

64.2

63.4

63.2

61.5

61.0

60.7

57.3

55.9

55.6

54.0

51.6

49.9

32.2

31.8

31.7

31.2

30.8

29.1

28.6

27.8

27.1

26.7

0.0063

0.0679

0.0316

0.0362

0.0588

0.0649

0.0593

0.0040

0.1286

0.0013

0.0027

0.0006

0.0197

0.0387

0.0005

0.0119

0.0073

0.3505

0.3906

0.2631

0.0268

0.0298

1.0054

0.0076

0.0394

0.4434

0.1134

0.0016

0.0042

0.0008

0.0137

0.0975

0.0475

0.1456

0.0080

0.0745

0.1713

0.0050

0.0034

0.0022

1→5; 8→10

1→7; 8→12

1→9; 7→9

1→10; 8→13,7→11

1→11; 8→13,7→11

1→13; 8→9

1→15; 8→11 ,6→11

1→17; 6→9

1→21; 8→11 ,6→11

1→23; 7→23

1→25; 5→10

1→28; 7→12

1→30; 5→13

1→33; 5→12. 4→10

1→35; 7→13

1→38; 6→10

1→39; 5→9

1→41; 5→12,4→10

1→42; 4→12

1→43; 3→9

1→45; 6→12

1→46; 3→11

1→49; 4→9

1→51; 6→13

1→52; 4→11

1→54; 3→11

1→55; 4→13

1→57; 3→10

1→59; 3→12

1→61; 3→13

1→66; 2→9,2→10

1→67; 2→12

1→68; 2→9,2→10

1→71; 2→13

1→72; 2→11

1→74; 1→9

1→75; 1→11

1→77; 1→10

1→79; 1→12

1→81; 1→13

–24.547055634

aThe oscillator strength

Figure 6. Changes of the electron density in the carbon dioxide molecule prior to (left) and after applica-

tion (right) of the field of 0.01 a.u.

J. Mazurkiewicz et al. / Natural Science 2 (2010) 1195-1210

1208

tions in the central part of the spectrum (transitions

1→17, 1→18 and 1→19). Applied electric field destabi-

lizes the system. Energy of destabilization is 0.038981738

a.u. i.e. the total energy of the molecule in the field is

higher than the total energy of field-unperturbed mole-

cule.

Figure 7 presents mapping of isosurface of the am-

monia molecule in unperturbed state and after its expo-

sure to the 0.01 a.u. electric field.

Applied electric field concentrates the charge on the

lone electron pair orbital of the nitrogen atom making

ammonia a stronger base. Corresponding data showed

that the negative charge on the nitrogen atom declined

from –0.415 into -0.420.

Totally 80 transitions were analyzed on simulation of

the UVVIS spectrum of the ammonia-water system (Ta-

ble 5). Forty of them appears active in the spectra with-

out and with the field of 0.01 a.u. Because in the electric

field water and ammonia turn into stronger acid and base,

respectively, their mutual interactions introduce a com-

plex spectral changes. Only in the most blue part of the

spectrum these changes appear minute.

The electric field of 0.01 a.u. destabilized also this sys-

tem. The energy of destabilization reaching 0.019963162

a.u. is lower than that in single ammonia molecule

placed in this field.

Figure 8 presents mapping of isosurface of the am-

monia – water system

One can see that in that system out of the electric field

the negative charge (–0.432) is more pronounced at the

nitrogen atom of ammonia than at the oxygen atom of

the partnering water molecule (–0.428). After the appli-

cation of the 0.01 a.u. electric field, the negative charge

is more concentrated at the water oxygen atom (–0.452)

than at the ammonia nitrogen atom (-0.420). It provides

an evidence that in the electric field enhanced acidic and

basic properties of water and ammonia molecules, re-

spectively, result in the acid-base interactions in which

water is hydrogen donor and ammonia its acceptor.

Thus, except CO2, all investigated single small mole-

cules out of aura emit UV light in the area of the vacuum

ultraviolet. In the spectrum of CO2 one weak transition

appears at 221.1 in order to cease after application of the

0.01 a.u. electric field. In the system of two molecules

checked for nitrogen the first transitions appear at 180.4

and 169.6 nm, however, they are very weak. The transi-

Figure 7. Mapping of isosurface of the ammonia molecule in unperturbed state and after its

exposure to the 0.01 a.u. electric field.

Figure 8. Mapping of isosurface of the ammonia water molecules system in unperturbed state (two left images) and after its

exposure (two right images) to the 0.01 a.u. electric field.

J. Mazurkiewicz et al. / Natural Science 2 (2010) 1195-1210

1209

tions of the intensity comparable to these in the spectrum

of the single nitrogen molecule are met also at 100 nm.

In the spectrum of two oxygen molecules the first inten-

sive transition resides at the wavelength by 16 nm higher

than in the spectrum of the single molecule. However,

majority of the shorter wavelength transitions com-

pletely ceases. The spectrum of two CO2 entirely differ

from the spectrum of the single molecule. Anyway, the

longest wavelength transitions disappears. Further in-

crease in the number of molecules in the systems

checked for N2, O2 and H2O provides diverse results. In

the spectra of five nitrogen and five water molecules the

longest wavelength transitions seen in their spectrum of

two molecules are now absent. In contrast to them in the

spectrum of five O2 molecules longwavelength transi-

tions are added.

The effect of the electric field and on a given mole-

cule and their sets depends on the energy of the field and

it is not linear in that energy. Moreover, that effect is

specific for particular molecules. Only in the spectrum

of (O2)5 the electric field of 0.01 a.u. can generate long-

wavelength transitions beyond the vacuum ultraviolet

region. Also in the spectrum of N2 in the field of 0.05 a.u.

a weak transition at 202.2 nm can be seen. In no case

emission in the visible region can be found.

Since all transitions of the molecules under considera-

tions situated in the electric field are observed in the

vacuum ultraviolet region only spectrum of oxygen

would be observed for genuine plasma containing all the

molecules considered in this project.

4. CONCLUSIONS

Electric field over surfaces of inanimate objects rather

insignificantly change the electronic transitions in the

molecules constituting aura (N2, O2, H2O, CO2 and NH3).

All these molecules emit in the region of vacuum ultra-

violet. Only a system of 5 oxygen molecules in the field

of 0.01 a.u. exhibits weak transitions above 200 nm.

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