Äîêóìåíò âçÿò èç êýøà ïîèñêîâîé ìàøèíû. Àäðåñ îðèãèíàëüíîãî äîêóìåíòà : http://rswater.phys.msu.ru/Assets/Water/OptSpec_2010.pdf Äàòà èçìåíåíèÿ: Wed Sep 5 15:43:30 2012 Äàòà èíäåêñèðîâàíèÿ: Mon Oct 1 19:45:42 2012 Êîäèðîâêà:

, 2010, 109, 2, . 306­312


535.33


© 2010 . . . , . . , . .
. .. , 119991 , E mail: burikov@lid.phys.msu.ru
22.04.2009 . 12.02.2010 .

. 20 99° D2O KI, KBr, KCl KF . . .

() , , , [1, 2]. [3­12], ­ 3000­3800 ­1. , () . [11] , , . . [7, 8] " ". [13­15] , . , . [3­ 6, 9, 10] [2­11, 13­17]. , [2­6, 9, 10], (. 1).

(" " u ) (s) () . V. s a s in, s out a in, a out. s a. 2 in 2 out, 22 in 22 out. , [2]. s in 22 in 's - in 2 '2s - in 3 in, s out 22
out

's

out



2 '2s o ut 3 out. a in, a out , [2].

[2]. , , [2] ,

306




307

u

V
a



1



s

a

s a


out

2a


in

2s

d
s in

a

s

out

2

2 out


s out

0 out

2

2 in 0 in

W

'

3 out

'

s in

2'
3 in

2 out

2'

2 in


. 1. . , ­ .

: (H0 + W) = , (1) H0 ­ "" , W ­ , ­ . (1) , E1,2 :
0 0 E1,2 = [ E10 + E 2 ± ( E10 - E 2 )2 + 4W 2]/ 2 ,

(2)

( ­ E = 0 ­ , , ..

E10

0 2)

E1,2 =


0 (E10 + E 2 ) ± (/ 2), 2

(3)

2 2 (4) = 0 + 4W ­ . , W ( ), 0. E1, 2, .

( ) 2­4 . , ( ) . : I/I = I1/I2 = ( + 0)/( ­ 0). (5) , R = I 1/ I 2 = ( + 0) / ( - 0) (6) = 2 + 4W 2. 0 0 . , . W . . [4­6] W (6) . 4 ,
2010



109

2

9*


308

.

1. (W), (V) () H2O [4, 5], H2O [6], LiCl, 12m [9, 10] [11] [16] [17] W, ­1 97 70 99.5 36 151 83.5 V, ­1 23 32 ­ ­ ­ , ­1 96 42 ­ ­ ­

. . 1000 8000 ­1. ( 488 , 450 ). 90 (Acton 2500i, 2 ­1), Hamamatsu H 8259 01, , CCD . 30 99° KI, KBr, KCl KF ( 0 4­6 0.4 ) HDO ( D2O H2O 0 100 % 5­10 %). (7) : Iiso = I|| ­ (4/3)I, Ianiso = (4/3)I, (7) I|| I ­ . . 2 1400­ 3800 ­1. , , , [1, 3, 12, 13, 18, 19]. 20 99° 47 ­1, KI ­ 61 ­1, KBr ­ 48 ­1, KCl ­ 38 ­1, KF ­ 5 ­1 ( KF ) [12, 18­20]. [1, 3, 12, 13] [18­20]. ,
109 2 2010

. , 2 ( 3210 3405 ­1) . R = = I1/I2, (6) 0 W. [9, 10] , , , . , R W , ( 3250­3350 ­1) . . . 1 W, (V) () H2O. [11, 16, 17] W , [4, 6, 9, 10] . . 1, Ñ W ­ . , . KI, KBr, KCl KF, ­






309

( 1.5­2 ) [19, 20]. 20 99° 8 ­1 , 2, 4, 12 ­1 KI, KBr, KCl (. 3) [19, 20]. "" [20]. W. W R ­ (4). W ("" ) ("" ). "" H2O "" H2O D2O. , HOD H2O , .. , , . , s iso x anixo ma ma H2O D2O (. 4). (. 4), s iso x(CH2O) anixo(CH2O) ma ma u 10 % H2O D2O max = = (3430 ± 2) ­1. "" . ""
109 2 2010

, . .
1.0

1.2
0.6 0.2

0.8

1400

1600

1800

0.4

0

1600

2400

3200 ,

-1

. 2. KCl ( ­ ): ( ); KCl, 1.2 ( ); KCl, 2.8 ( ).

, - 1700 ()

1

1600

1500

1400 1650

30

50 ()

70

90 , °C

1640

1630

1620

0

2

4 6 , M

. 3. () ( ­ HDO, ­ H2O), () ( ­ KI, ­ KBr, ­ KCl).


310 , - 3480 3460 3440 3420 3400 3380
1

.

, . [4], , , C2v (, s), . , , ( ) C2v ( 3645 ­1). , . . [22] . , . . 2. " " , u : 1Gauss < 2 2 = 3238 ­1; u 3Gauss > max = u l = 3430 ­1. va : 3­4 ­1 . , "" : u : 2 2 = (3238 ± 4) c­1; : u l = (3430 ± 2) ­1 va (. 4). "" 1Gauss 3Gauss, (. 2).
109 2 2010

0

40

80

CH2O, %

max (CH2O) ( ) s anixo (CH2O) ( ). ma
iso

. 4. «» u l = 3430 ­1 () va

OH ( HDO) . , HDO 10 % H2O D2O 50 % H2O D2O 97° 1634­1638 ­1. 2 = (1636 ± 2) c­1. "" , . 22 = ­17.04 ­1, [21]. "" u 2 = (1619 ± 2) c­1, " u " 2 2 = (3238 ± 4) c­1. "" H2O , . ,






311

2. H2O, 20° KCl, 4 KBr, 4 KBr, 5 M KI, 4 KF, 5 KF, 10 KF, 13 H2O, 30 ° H2O, 50 ° H2O
1Gauss

W, ­1 58 37 35 28 14 58 62 62 43 30 ± ± ± ± ± ± ± ± ± ± 9 8 8 8 8 8 8 8 9 8

I



/I



= 22 , ± ± ± ± ± ± ± ± ± ± 4 3 3 3 3 3 3 3 4 3

­1



3Gauss

, ± ± ± ± ± ± ± ± ± ± 4 3 3 3 3 3 3 3 4 3

­1

3210 3239 3256 3260 3287 3206 3210 3212 3210 3229

3434 3445 3460 3460 3481 3430 3438 3440 3420 3430

13 28 3 49 193 13 12 12 22 44

(4). W = (58 ± 9) ­1. . 2. W, "" , 9 ­1 8 ­1 . , 0 4­5 KBr, KCl KI 1.5­4 (. 2). W KI, , . , . , . , 0 , . KF W . . , ,
109 2

, .. . , , . W . . , , . , W . (. 1) , . "" "" . (5) ­ "" "" . . 2 .
2010


312

.

"" 3210 ­1 1/13 (8%) "" 3434 ­1. , 2v, , 10% . , . . , "" (. 2). W . , , W, , . ­ , ­ . "" " " 0 , "" , . ,

. .. .
1. ., . : .: , 1975. 279 c. 2. .., .. . : , 1984. C. 11. 3. Scherer J.R. // Advances in Infrared and Raman Spec troscopy / Ed. by Clark R.J.H., Hoster R.E. London: Hayden, 1978. V. 5. P. 149. 4. Sokolowska A., Kecki Z. // J. Raman Spectrosc. 1986. V. 17. P. 29. 5. Sokolowska A. // J. Raman Spectrosc. 1989. V. 20. P. 779. 6. Sokolowska A., Kecki Z. // J. Mol. Str. 1983. V. 101. 1­2. P. 113. 7. Efimov Yu.Ya., Naberukhin Yu.I. // Spectrochimica Acta. A. 2002. V. A58. P. 519. 8. .. // . . . 2001. . 42. 6. . 1122. 9. Zhelyaskov V., Georgiev G., Nickolov Zh., Miteva M. // Mol. Phys. 1988. V. 64. 6. P. 1133. 10. Zhelyaskov V., Georgiev G., Nickolov Zh. // J. Raman Spectrosc. 1988. V. 19. P. 405. 11. Smith D.F., Overend J. // Spectrochimica Acta. A. 1972. V. 28. P. 471. 12. Dolenko T.A., Churina I.V., Fadeev V.V., Glushkov S.M. // J. Raman Spectrosc. 2000. V. 31. P. 863. 13. Walrafen G. // Water: A Comprehensive Treatise / Ed. by Franks F. N.Y.: Plenum, 1972. V. 1. P. 151. 14. Giguere P.A. // J. Raman Spectrosc. 1984. V. 15. P. 354. 15. Belch A., Rice S. // J. Chem. Phys. 1983. V. 78. P. 4317. 16. Pariseau M.A. Thesis, University of Minnesota. USA, 1963. 17. Hoy A.R., Mills I.M., Strey G. // Mol. Phys. 1972. V. 24. P. 1265. 18. .., .., .., .., .. // . . 2005. . 98. 2. . 235. 19. Burikov S.A., Dolenko T.., Fadeev V.V., Vlasov I.I. // Las. Phys. 2007. V. 17. 9. P. 1. 20. .. . . . ., 2008. 21. .., .., .. . .: , 1970. 422 . 22. Goldberg D.E. Genetic Algorithms in Search, Optimi zation, and Machine learning. USA: Addison Wesley Publishing Co., 1989. 442 p.
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