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INTRAMOLECULAR DYNAMICS IN XINTRAMOLECULAR DYNAMICS IN X4 4
CYCLIC CLUSTERSCYCLIC CLUSTERS
Roberto Linguerri Laboratoire de Chimie Théorique,
Université de Marne la Vallée,
F - 77454 Champs sur Marne, France
DOUBLE MINIMUM IN BDOUBLE MINIMUM IN B44
1Ag
CYCLOBUTADIENECYCLOBUTADIENE
For instance: A. Balkova and R. J. Bartlett, J. Chem. Phys. 101, 8972 (1994).
R. L. Redington, J. Chem. Phys. 109, 10781 (1998).
AB INITIO TREATMENTAB INITIO TREATMENT
ELECTRONIC STRUCTURE
CCSD(T) MOLPRO
VIBRATIONAL LEVELS
VCI MULTIMODE
COORDINATE SYSTEMCOORDINATE SYSTEM
CONTOUR CUT OF THE 6D PESCONTOUR CUT OF THE 6D PES
E= 2000 cm-1
s= 50 cm-1
PSEUDOROTATION ?PSEUDOROTATION ?
PSEUDOROTATION ?PSEUDOROTATION ?
Ag
NORMAL MODES IN RHOMBIC BNORMAL MODES IN RHOMBIC B44
B2uB3u
B1gB1uAg
HARMONIC FREQUENCIESHARMONIC FREQUENCIES
B4 rhombus B4 square
1 / cm-1 1142 Ag 1143 A1g
2 / cm-1 311 Ag 209 i B1g
3 / cm-1 1216 B1g 1240 B2g
4 / cm-1 304 B1u 272 B2u
5 / cm-1 1013 B2u 1148 Eu
6 / cm-1 1235 B3u 1148 Eu
level 11B4 41.2% 10B11B3 40.9%
ZPE/cm-1 2352 (22) D4h 2364 (23) C2v
1 / cm-1 1136 (24) A1g 1148 (24) A1
2 / cm-1 209 (144) B1g 212 (148) A1
3 / cm-1 1198 (19) B2g 1218 (21) B2
4 / cm-1 271 (24) B2u 274 (25) B1
5 / cm-1 1030 (166)
Eu
1041 (158) A1
1042 (160) B2
ANHARMONIC FUNDAMENTAL VIBRATIONAL ANHARMONIC FUNDAMENTAL VIBRATIONAL LEVELS OF LEVELS OF 1111BB44 AND AND 1010BB1111BB33
CUTS OF THE 6D VIBRATIONAL WAVE CUTS OF THE 6D VIBRATIONAL WAVE FUNCTION ALONG THE SQUEEZING FUNCTION ALONG THE SQUEEZING
AND OUT OF PLANE MODESAND OUT OF PLANE MODES
QAg
QB1u
CUTS OF THE 6D VIBRATIONAL WAVE CUTS OF THE 6D VIBRATIONAL WAVE FUNCTION ALONG THE SQUEEZING FUNCTION ALONG THE SQUEEZING
AND OUT OF PLANE MODESAND OUT OF PLANE MODES
QAg
QB1u
TIME DEPENDENT MOLECULAR TIME DEPENDENT MOLECULAR DYNAMICSDYNAMICS
MCTDH
• Relaxation of a wavepacket
• Application of an excitation operator added an energy of 27 cm-1
• Following propagation
JACOBIAN COORDINATES FOR BJACOBIAN COORDINATES FOR B44
SiCSiC3 3 CYCLIC CLUSTERCYCLIC CLUSTER
For instance: M. C. McCarthy, A. J. Apponi, and P. Thaddeus, J. Chem. Phys. 110, 10645 (1999).
M. C. McCarthy, A. J. Apponi, and P. Thaddeus, J. Chem. Phys. 111, 7175 (1999).
Si
C
C
C
C
C
C
Si
Laboratoire de Chimie Laboratoire de Chimie Théorique EA 2180Théorique EA 2180
Université de Marne la ValléeUniversité de Marne la Vallée
Pavel Rosmus
Pr-MLV 1993
Isabelle Navizet
MdC-MLV 2005
R. Linguerri, I. Navizet, P. Rosmus, S. Carter, and J. P. Maier, J. Chem. Phys. 122, 34301 (2005).