intramolecular dynamics in x 4 cyclic clusters roberto linguerri laboratoire de chimie théorique,...

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).