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ON THE DETERMINATION OF RATE CONSTANTS FROM EQUILIBRIUM MOLECULAR-DYNAMICS SIMULATIONS
被引:21
作者
:
BROWN, D
论文数:
0
引用数:
0
h-index:
0
机构:
Chemistry Department, U.M.I.S.T., Manchester M60 1QD, Sackville Street
BROWN, D
CLARKE, JHR
论文数:
0
引用数:
0
h-index:
0
机构:
Chemistry Department, U.M.I.S.T., Manchester M60 1QD, Sackville Street
CLARKE, JHR
机构
:
[1]
Chemistry Department, U.M.I.S.T., Manchester M60 1QD, Sackville Street
来源
:
JOURNAL OF CHEMICAL PHYSICS
|
1990年
/ 93卷
/ 06期
关键词
:
D O I
:
10.1063/1.458744
中图分类号
:
O64 [物理化学(理论化学)、化学物理学];
学科分类号
:
070304 ;
081704 ;
摘要
:
In this article we consider the calculation of rate constants from equilibrium molecular dynamics simulations using the conformational isomerization in liquid butane as an example. In particular we discuss the method by which transition state theory estmates of the rate constant may be calculated from simulation data. Care has to be taken when calculating the average velocity along the reaction coordinate at the barrier. If this is computed just from actual barrier crossings we show that there is a systematic overestimation by a factor of exactly π/2. Further analysis has allowed the connection between the barrier crossing rate and the transition state theory value for the rate constant to be established. We compare rate constants determined by the "reactive flux" method with values obtained using alternative approaches applied to liquid n-butane [D. Brown and J. H. R. Clarke, J. Chem. Phys. 92, 3062 (1990)]. The results of this comparison have implications regarding the identification of the plateau value when using the reactive flux method. A straightforward procedure is described which can establish confidence limits for rate constants calculated in this way. © 1990 American Institute of Physics.
引用
收藏
页码:4117 / 4122
页数:6
相关论文
共 10 条
[1]
Allen M.P., 1987, COMPUTER SIMULATION
[2]
MOLECULAR-DYNAMICS OF A MODEL SN2 REACTION IN WATER
BERGSMA, JP
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV CALIF SAN DIEGO,DEPT CHEM,LA JOLLA,CA 92093
BERGSMA, JP
GERTNER, BJ
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV CALIF SAN DIEGO,DEPT CHEM,LA JOLLA,CA 92093
GERTNER, BJ
WILSON, KR
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV CALIF SAN DIEGO,DEPT CHEM,LA JOLLA,CA 92093
WILSON, KR
HYNES, JT
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV CALIF SAN DIEGO,DEPT CHEM,LA JOLLA,CA 92093
HYNES, JT
[J].
JOURNAL OF CHEMICAL PHYSICS,
1987,
86
(03)
: 1356
-
1376
[3]
A DIRECT METHOD OF STUDYING REACTION-RATES BY EQUILIBRIUM MOLECULAR-DYNAMICS - APPLICATION TO THE KINETICS OF ISOMERIZATION IN LIQUID NORMAL-BUTANE
BROWN, D
论文数:
0
引用数:
0
h-index:
0
机构:
Chemistry Department, U.M.I.S.T., Manchester M60 1QD, Sackville Street
BROWN, D
CLARKE, JHR
论文数:
0
引用数:
0
h-index:
0
机构:
Chemistry Department, U.M.I.S.T., Manchester M60 1QD, Sackville Street
CLARKE, JHR
[J].
JOURNAL OF CHEMICAL PHYSICS,
1990,
92
(05)
: 3062
-
3073
[4]
STATISTICAL-MECHANICS OF ISOMERIZATION DYNAMICS IN LIQUIDS AND TRANSITION-STATE APPROXIMATION
CHANDLER, D
论文数:
0
引用数:
0
h-index:
0
机构:
COLUMBIA UNIV,DEPT CHEM,NEW YORK,NY 10027
COLUMBIA UNIV,DEPT CHEM,NEW YORK,NY 10027
CHANDLER, D
[J].
JOURNAL OF CHEMICAL PHYSICS,
1978,
68
(06)
: 2959
-
2970
[5]
CONFORMATIONAL KINETICS IN LIQUID BUTANE BY NONEQUILIBRIUM MOLECULAR-DYNAMICS
EDBERG, R
论文数:
0
引用数:
0
h-index:
0
EDBERG, R
EVANS, DJ
论文数:
0
引用数:
0
h-index:
0
EVANS, DJ
MORRISS, GP
论文数:
0
引用数:
0
h-index:
0
MORRISS, GP
[J].
JOURNAL OF CHEMICAL PHYSICS,
1987,
87
(10)
: 5700
-
5708
[6]
STOCHASTIC MOLECULAR-DYNAMICS STUDY OF TRANS-GAUCHE ISOMERIZATION PROCESSES IN SIMPLE CHAIN MOLECULES
MONTGOMERY, JA
论文数:
0
引用数:
0
h-index:
0
MONTGOMERY, JA
HOLMGREN, SL
论文数:
0
引用数:
0
h-index:
0
HOLMGREN, SL
CHANDLER, D
论文数:
0
引用数:
0
h-index:
0
CHANDLER, D
[J].
JOURNAL OF CHEMICAL PHYSICS,
1980,
73
(08)
: 3688
-
3694
[7]
Pechukas P., 1976, DYNAMICS MOL COLLISI
[8]
ISOMERIZATION DYNAMICS IN LIQUIDS BY MOLECULAR-DYNAMICS
ROSENBERG, RO
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV ILLINOIS,SCH CHEM SCI,URBANA,IL 61801
UNIV ILLINOIS,SCH CHEM SCI,URBANA,IL 61801
ROSENBERG, RO
BERNE, BJ
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV ILLINOIS,SCH CHEM SCI,URBANA,IL 61801
UNIV ILLINOIS,SCH CHEM SCI,URBANA,IL 61801
BERNE, BJ
CHANDLER, D
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV ILLINOIS,SCH CHEM SCI,URBANA,IL 61801
UNIV ILLINOIS,SCH CHEM SCI,URBANA,IL 61801
CHANDLER, D
[J].
CHEMICAL PHYSICS LETTERS,
1980,
75
(01)
: 162
-
168
[9]
ANDERSEN CANONICAL-ENSEMBLE MOLECULAR-DYNAMICS FOR MOLECULES WITH CONSTRAINTS
RYCKAERT, JP
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV CAMBRIDGE,DEPT PHYS CHEM,CAMBRIDGE CB2 1EP,ENGLAND
RYCKAERT, JP
CICCOTTI, G
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV CAMBRIDGE,DEPT PHYS CHEM,CAMBRIDGE CB2 1EP,ENGLAND
CICCOTTI, G
[J].
MOLECULAR PHYSICS,
1986,
58
(06)
: 1125
-
1136
[10]
MOLECULAR-DYNAMICS OF LIQUID ALKANES
RYCKAERT, JP
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV LIBRE BRUXELLES, FAC SCI, B-1050 BRUSSELS, BELGIUM
UNIV LIBRE BRUXELLES, FAC SCI, B-1050 BRUSSELS, BELGIUM
RYCKAERT, JP
BELLEMANS, A
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV LIBRE BRUXELLES, FAC SCI, B-1050 BRUSSELS, BELGIUM
UNIV LIBRE BRUXELLES, FAC SCI, B-1050 BRUSSELS, BELGIUM
BELLEMANS, A
[J].
FARADAY DISCUSSIONS,
1978,
66
: 95
-
106
←
1
→
共 10 条
[1]
Allen M.P., 1987, COMPUTER SIMULATION
[2]
MOLECULAR-DYNAMICS OF A MODEL SN2 REACTION IN WATER
BERGSMA, JP
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV CALIF SAN DIEGO,DEPT CHEM,LA JOLLA,CA 92093
BERGSMA, JP
GERTNER, BJ
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV CALIF SAN DIEGO,DEPT CHEM,LA JOLLA,CA 92093
GERTNER, BJ
WILSON, KR
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV CALIF SAN DIEGO,DEPT CHEM,LA JOLLA,CA 92093
WILSON, KR
HYNES, JT
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV CALIF SAN DIEGO,DEPT CHEM,LA JOLLA,CA 92093
HYNES, JT
[J].
JOURNAL OF CHEMICAL PHYSICS,
1987,
86
(03)
: 1356
-
1376
[3]
A DIRECT METHOD OF STUDYING REACTION-RATES BY EQUILIBRIUM MOLECULAR-DYNAMICS - APPLICATION TO THE KINETICS OF ISOMERIZATION IN LIQUID NORMAL-BUTANE
BROWN, D
论文数:
0
引用数:
0
h-index:
0
机构:
Chemistry Department, U.M.I.S.T., Manchester M60 1QD, Sackville Street
BROWN, D
CLARKE, JHR
论文数:
0
引用数:
0
h-index:
0
机构:
Chemistry Department, U.M.I.S.T., Manchester M60 1QD, Sackville Street
CLARKE, JHR
[J].
JOURNAL OF CHEMICAL PHYSICS,
1990,
92
(05)
: 3062
-
3073
[4]
STATISTICAL-MECHANICS OF ISOMERIZATION DYNAMICS IN LIQUIDS AND TRANSITION-STATE APPROXIMATION
CHANDLER, D
论文数:
0
引用数:
0
h-index:
0
机构:
COLUMBIA UNIV,DEPT CHEM,NEW YORK,NY 10027
COLUMBIA UNIV,DEPT CHEM,NEW YORK,NY 10027
CHANDLER, D
[J].
JOURNAL OF CHEMICAL PHYSICS,
1978,
68
(06)
: 2959
-
2970
[5]
CONFORMATIONAL KINETICS IN LIQUID BUTANE BY NONEQUILIBRIUM MOLECULAR-DYNAMICS
EDBERG, R
论文数:
0
引用数:
0
h-index:
0
EDBERG, R
EVANS, DJ
论文数:
0
引用数:
0
h-index:
0
EVANS, DJ
MORRISS, GP
论文数:
0
引用数:
0
h-index:
0
MORRISS, GP
[J].
JOURNAL OF CHEMICAL PHYSICS,
1987,
87
(10)
: 5700
-
5708
[6]
STOCHASTIC MOLECULAR-DYNAMICS STUDY OF TRANS-GAUCHE ISOMERIZATION PROCESSES IN SIMPLE CHAIN MOLECULES
MONTGOMERY, JA
论文数:
0
引用数:
0
h-index:
0
MONTGOMERY, JA
HOLMGREN, SL
论文数:
0
引用数:
0
h-index:
0
HOLMGREN, SL
CHANDLER, D
论文数:
0
引用数:
0
h-index:
0
CHANDLER, D
[J].
JOURNAL OF CHEMICAL PHYSICS,
1980,
73
(08)
: 3688
-
3694
[7]
Pechukas P., 1976, DYNAMICS MOL COLLISI
[8]
ISOMERIZATION DYNAMICS IN LIQUIDS BY MOLECULAR-DYNAMICS
ROSENBERG, RO
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV ILLINOIS,SCH CHEM SCI,URBANA,IL 61801
UNIV ILLINOIS,SCH CHEM SCI,URBANA,IL 61801
ROSENBERG, RO
BERNE, BJ
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV ILLINOIS,SCH CHEM SCI,URBANA,IL 61801
UNIV ILLINOIS,SCH CHEM SCI,URBANA,IL 61801
BERNE, BJ
CHANDLER, D
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV ILLINOIS,SCH CHEM SCI,URBANA,IL 61801
UNIV ILLINOIS,SCH CHEM SCI,URBANA,IL 61801
CHANDLER, D
[J].
CHEMICAL PHYSICS LETTERS,
1980,
75
(01)
: 162
-
168
[9]
ANDERSEN CANONICAL-ENSEMBLE MOLECULAR-DYNAMICS FOR MOLECULES WITH CONSTRAINTS
RYCKAERT, JP
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV CAMBRIDGE,DEPT PHYS CHEM,CAMBRIDGE CB2 1EP,ENGLAND
RYCKAERT, JP
CICCOTTI, G
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV CAMBRIDGE,DEPT PHYS CHEM,CAMBRIDGE CB2 1EP,ENGLAND
CICCOTTI, G
[J].
MOLECULAR PHYSICS,
1986,
58
(06)
: 1125
-
1136
[10]
MOLECULAR-DYNAMICS OF LIQUID ALKANES
RYCKAERT, JP
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV LIBRE BRUXELLES, FAC SCI, B-1050 BRUSSELS, BELGIUM
UNIV LIBRE BRUXELLES, FAC SCI, B-1050 BRUSSELS, BELGIUM
RYCKAERT, JP
BELLEMANS, A
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV LIBRE BRUXELLES, FAC SCI, B-1050 BRUSSELS, BELGIUM
UNIV LIBRE BRUXELLES, FAC SCI, B-1050 BRUSSELS, BELGIUM
BELLEMANS, A
[J].
FARADAY DISCUSSIONS,
1978,
66
: 95
-
106
←
1
→