Äîêóìåíò âçÿò èç êýøà ïîèñêîâîé ìàøèíû. Àäðåñ îðèãèíàëüíîãî äîêóìåíòà : http://www.mce.biophys.msu.ru/archive/doc15614/doc.pdf Äàòà èçìåíåíèÿ: Wed Oct 24 19:26:52 2007 Äàòà èíäåêñèðîâàíèÿ: Mon Oct 1 20:28:11 2012 Êîäèðîâêà: Ïîèñêîâûå ñëîâà: m 15

- . ., . .

(, )
- H2O. . . , , .

, [1,2]. ? ? , - . , , 280 . [3]. {H2O}280 {H2O}14 {H2O}20. [4] [5]. [6], . {H2O}160, (2·{H2O}20+2·{H2O}60) [7,8].


8. , Part 8. Mathematical methods in biology, ecology and chemistry

. 1. - NH

4

+

{H2O}20 H3O+{H2O}20

- . - , . . Gaussian 03 [9]. 1114


. ., . . -- -- 2005, . 3, . 1113 ­ 1115 Kargovsky A. V., Mitrofanov V. V. -- MCE -- 2005, vol. 3, p. 1113 ­ 1115

6-31G** c - . . 1 - H3O+{H2O}20 NH4+{H2O}20, , . : · 50 ­ 900 ­1 ; · 1450 - 1800 ­1 -- · 3500 - 4000 ­1 -- . H3O+{H2O}20 ~1212 -1, -, ( ­NH4+{H2O}20, Na+{H2O}20, K+{H2O}20 ­ ). . . (-H2O) (-H2O) . , -H2O (.. -H2O [10]). . : r rr U = (r ) (r )dr , r r2 r (r ) = 10e (r ) + (r ) -- r , (r ) -- , . : ^^ ^ H = T + U .
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8. , Part 8. Mathematical methods in biology, ecology and chemistry

-- , . : h2 ^ 2 h2 ^ 2 h2 ^ 2 ^ T = J + J + J , 2I A 2I B 2 IC ^^^ J , J , J --

; I A , I B , I C -- . , ( I A I B I C ) . J [11]: J 2J + 1 J n ( (JM) = ckn ) JMk , JMk = i J DkM ( , , ) , 8 2 k =- J
J DkM ( , , ) -- D- [12]; , , -- , , (n) ; ck -

= En (Jn ) . M . , n- [11]: ^ En = ( n ) U ( n ) .
(n) JM

^ T

«» . D- [12]:
J DkM (1 , 1 , 1 ) = M =- J



J

J DkJM ( A, , ) DM M ( , , ) ,

1 , 1 , 1 -- ; A, , -- , ; , , -- , .
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. ., . . -- -- 2005, . 3, . 1113 ­ 1117 Kargovsky A. V., Mitrofanov V. V. -- MCE -- 2005, vol. 3, p. 1113 ­ 1117

2 J + 1 J (n) J J ck M J DkJM ( A, , ) DM M ( , , ) . 8 2 k =- J =- , , . D , ,
(n) JM

=i

J

U ( ) =

J = 0 k = - J M = - J


2



J

J



J k M

DkJM ( ) ,



J k M

=

2J + 1 * d d d sin U ( , , ) DkJM ( , , ) , 8 2 0 0 0

2



J J 2J +1 J J c(n)c(n)* DkJM ()DMM ()DkJ* ()DM*M ()U()dd . M 2 k k 8 k,k=-J M,M=-J . D- , 2 J + 1 J (n) 2 J J J* En = ck M J DMM ( ) DMM ( )U ( )d . 8 2 k =- J = - JMk , :

En =

2J + 1 J J J J DM M ( ) DM*M ( )U ( )d . 2 8 M =- k =- J D- [12]: J* J DMM ( ) = (-1) M - M D- M - M ( ) ,



J

( ck

n) 2

=1 En =


C

J J J DM11M1 ( ) DM22 M 2 ( ) DM33M3 ( )d = (-1)

M3 - M3

8 2 - - CJJ3M M3M CJJ3M M3M . J J 2J3 + 1 1 1 2 2 1 1 2 2

J3M 3 J1M1 J 2 M

2

-- -. M

- :
0 C JJMJ - M C JJM 0J - M . 2J + 1 , 2 2 (2 J + 1) 2 0 En = (2 J + 1) 00 = 2 d d d sin U ( , , ) . 8 0 0 0

En = (2 J + 1)(-1)

M =- J



J

(-1)

M

J = 0



2J



J 00

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8. , Part 8. Mathematical methods in biology, ecology and chemistry

, , , . J 1, 4J + 3 , = U ( )d 8h 2 . «» . . . - [13, 14]. «» 264 , . «», . , . 30 a.e.., . , , , , , . 50­1000 ·­1·å­2, 1012­1013 . SP3- [15, 16]. NVT T = 298 K. Verlet 0.2 . Modyp, KAMA Group MSU Molecular Design and Modelling Laboratory [17]. () , [15].
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. ., . . -- -- 2005, . 3, . 1113 ­ 1119 Kargovsky A. V., Mitrofanov V. V. -- MCE -- 2005, vol. 3, p. 1113 ­ 1119

: OSC-H 1). OSC-O = O-O = 0.15 -- , = H-H = 0.02 , OSC-H -- 2). OSC-O = 5 O-O = 0.75 , = 5 H-H = 0.1 , 1 OSC-H 1 H-H -- 3). OSC-O = O-O = 0.03 , = = 0.004 5 5 . , , [15], , Q, , , Q = m/. . 2, . , -. , , , . (, «-») , .

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8. , Part 8. Mathematical methods in biology, ecology and chemistry

. 2. (), ( ) ( )

. 2. : () m = 30 ..., () m = 60 ..., () m = 15 ..

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. ., . . -- -- 2005, . 3, . 1113 ­ 1121 Kargovsky A. V., Mitrofanov V. V. -- MCE -- 2005, vol. 3, p. 1113 ­ 1121

-- «» 264 , , . 1.9 å, , , . -. : 1). U 2). U 3). U
OSC-B OSC-B OSC-B

=0.15 / -- «» =1.50 / -- «» =0.02 / -- «»

. , Q = m/. . 3. , , 1012Â1013 10Â450. .. , . . , , . , .

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8. , Part 8. Mathematical methods in biology, ecology and chemistry

. 3. Q() (N) , (S) (W) . -- SP3-

.. .. .
-2071.2003.4, 05-03-32880 . .. 2004 - 2005 .

: 1. Ludwig R. Water: From clusters to the bulk // Angew. Chem. Int. Ed. 2001. V.40. P.1808­1827. 2. .., .., .. // . 2003. .48. .1011­1021.
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3. Chaplin M.F. A proposal for the structuring of water // Biophys. Chem. 2000. V.83. P.211­221. 4. Sobott F., Wattenberg A., Barth H.D. and Brutschy B. Ionic clathrates from aqueous solutions detected with laser induced liquid beam ionization/desorption mass spectrometry // Int. J. Mass Spectr. 1999. V.185. P.271­279. 5. Steel E.A., Merz K.M., Selinger A. and Castleman A.W. Massspectral and computational free-energy studies of alkali-metal ion-containing water clusters // J. Phys. Chem. 1995. V.99. P.7829­7836. 6. Cameron I.L., Kanal K.M., Keener C.R. and Fullerton G.D. A mechanistic view of the non-ideal osmotic and motional behavior of intracellular water // Cell Biol. Int. 1997. V.21. P.99­113. 7. MÝller A., BÆgge H. and Diemann E. Structure of a cavityencapsulated nanodrop of water // Inorg. Chem. Commun. 2003. V.6. P.52­53. 8. MÝller A., Krickemeyer E., BÆgge H., Schmidtmann M., Roy S. and Berkle A. Changeable Pore Sizes Allowing Effective and Specific Recognition by a Molybdenum-Oxide Based "Nanosponge": En Route to Sphere-Surface and Nanoporous-Cluster Chemistry // Angew. Chem. Int. Ed. 2002. V.41. P.3604­3609. 9. Frisch M.J. et al. Gaussian 03, Revision B.03 -- Gaussian, Inc., Pittsburgh PA, 2003. 10. Tikhonov V.I. and Volkov A.A. Separation of water into its ortho and para-isomers // Science. 2002. V.296. P.2363. 11. .., .. . -- .: , 1989. 768c. 12. .., .., .. . -- .: , 1975. 439c. 13. Ebeling W., Schimansky-Geier L. and Romanovsky Yu. (eds.) Stochastic Dynamics of Reacting Biomolecules. -- Singapore: World Scientific, 2003. 329p. 14. Romanovsky Yu.M., Netrebko A.V. and Chikishev A.Yu. Are the Subglobular Oscillations of Protein Molecules in Water overdamped? // Laser physics. 2003. V.13. P.827­838.

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15. .., .. // . 2000. T.45. C.407­413. 16. Mitrofanov V.Vl., Romanovsky Yu.M. and Netrebko A.V. On the structure and dynamics of hydrogen bonds in liquid waterc// Proc. SPIE. 2004. V.5474. P.29­37. 17. Molecular Dynamic Modeling Pakage MoDyp© 1.14 built 1a -- - . : .. , .. .

IR-SPECTRA OF WATER CLUSTERS AND DUMPING OF THE FLUCTUATIONS OF ATOMIC GROUPS IN WATER ENVIRONMENT Kargovsky A. V., Mitrofanov V. V.
(Russia, Moscow) We consider transformation of vibrational IR-spectrum of water owing to formation of clusters from a small number of molecules H2O. Also an influence of H-bonds on rotational spectrum of water is considered. By means of molecular dynamics we analyze the problem of the dumping of atomic group fluctuations in water environment. It is shown that these fluctuations are not overdumped as it is predicted by Stokes theory.

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