Abstract
Kinematic effects arising from a metric and a gauge field in molecular internal space are studied in structural isomerization dynamics of three- and four-atom cluster with zero total angular momentum. The principal-axis hyperspherical coordinates (PAHC) are first employed to clarify both the mechanism of the isomerization reaction and associated kinematic effects. A force called "democratic centrifugal force" is obtained as a significant kinematic factor to dominate the isomerization dynamics. This force has an effect of inducing an asymmetry in mass balance of a system, and thereby brings about trapped motions in the vicinity of the transition states of the clusters coupling with the force arising from potential. We quantify the kinematic effects of a gauge field associated with the choice of Eckart frame, which is often disregarded in the conventional picture for molecular vibrations. Numerical study has revealed that the gauge field has an effect of suppressing the rate of isomerization reaction to a considerable amount. We also show mechanism of this suppressing effect in terms of the PAHC.
| Original language | English |
|---|---|
| Title of host publication | Advances in Chemical Physics |
| Publisher | Wiley Blackwell |
| Pages | 87-128 |
| Number of pages | 42 |
| Volume | 130 |
| ISBN (Print) | 9780471712534, 0471711586, 9780471711582 |
| DOIs | |
| Publication status | Published - 2005 May 12 |
| Externally published | Yes |
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Keywords
- Centrifugal force
- Cluster
- Eckart frame
- Falling cat
- Gauge field
- Hyperspherical coordinates
- Metric
- Normal mode
- Principal-axis frame
- Structural isomerization
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Effects of An Intrinsic Metric of Molecular Internal Space on Chemical Reaction Dynamics. / Yanao, Tomohiro; Takatsuka, Kazuo.
Advances in Chemical Physics. Vol. 130 Wiley Blackwell, 2005. p. 87-128.Research output: Chapter in Book/Report/Conference proceeding › Chapter
}
TY - CHAP
T1 - Effects of An Intrinsic Metric of Molecular Internal Space on Chemical Reaction Dynamics
AU - Yanao, Tomohiro
AU - Takatsuka, Kazuo
PY - 2005/5/12
Y1 - 2005/5/12
N2 - Kinematic effects arising from a metric and a gauge field in molecular internal space are studied in structural isomerization dynamics of three- and four-atom cluster with zero total angular momentum. The principal-axis hyperspherical coordinates (PAHC) are first employed to clarify both the mechanism of the isomerization reaction and associated kinematic effects. A force called "democratic centrifugal force" is obtained as a significant kinematic factor to dominate the isomerization dynamics. This force has an effect of inducing an asymmetry in mass balance of a system, and thereby brings about trapped motions in the vicinity of the transition states of the clusters coupling with the force arising from potential. We quantify the kinematic effects of a gauge field associated with the choice of Eckart frame, which is often disregarded in the conventional picture for molecular vibrations. Numerical study has revealed that the gauge field has an effect of suppressing the rate of isomerization reaction to a considerable amount. We also show mechanism of this suppressing effect in terms of the PAHC.
AB - Kinematic effects arising from a metric and a gauge field in molecular internal space are studied in structural isomerization dynamics of three- and four-atom cluster with zero total angular momentum. The principal-axis hyperspherical coordinates (PAHC) are first employed to clarify both the mechanism of the isomerization reaction and associated kinematic effects. A force called "democratic centrifugal force" is obtained as a significant kinematic factor to dominate the isomerization dynamics. This force has an effect of inducing an asymmetry in mass balance of a system, and thereby brings about trapped motions in the vicinity of the transition states of the clusters coupling with the force arising from potential. We quantify the kinematic effects of a gauge field associated with the choice of Eckart frame, which is often disregarded in the conventional picture for molecular vibrations. Numerical study has revealed that the gauge field has an effect of suppressing the rate of isomerization reaction to a considerable amount. We also show mechanism of this suppressing effect in terms of the PAHC.
KW - Centrifugal force
KW - Cluster
KW - Eckart frame
KW - Falling cat
KW - Gauge field
KW - Hyperspherical coordinates
KW - Metric
KW - Normal mode
KW - Principal-axis frame
KW - Structural isomerization
UR - http://www.scopus.com/inward/record.url?scp=33646518400&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33646518400&partnerID=8YFLogxK
U2 - 10.1002/0471712531.ch12
DO - 10.1002/0471712531.ch12
M3 - Chapter
AN - SCOPUS:33646518400
SN - 9780471712534
SN - 0471711586
SN - 9780471711582
VL - 130
SP - 87
EP - 128
BT - Advances in Chemical Physics
PB - Wiley Blackwell
ER -