SUBPICOSECOND TIME-RESOLVED IR SPECTROSCOPY OF THE VIBRATIONAL DYNAMICS OF RH(CO)2(ACAC)

被引:58
作者
BECKERLE, JD [1 ]
CASASSA, MP [1 ]
CAVANAGH, RR [1 ]
HEILWEIL, EJ [1 ]
STEPHENSON, JC [1 ]
机构
[1] NATL INST STAND & TECHNOL, GAITHERSBURG, MD 20899 USA
关键词
D O I
10.1016/0301-0104(92)80015-N
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
Sub-picosecond pulses are used to measure the transient IR spectra of vibrationally excited Rh(CO)2(acac) in dilute solutions of n-hexane and CCl3H. Ground-state bleach and excited-state absorption features are observed at t(D) > 0, while interference-like spectra characteristic of the perturbed free induction decay (FID) of the probe polarization are seen at t(D) < 0. At t(D) > 0, the bleach signal exhibits an initial decay (n-hexane, 3-6 ps; CCl3H, 2.2-4 ps) attributed to rapid v-v coupling between the symmetric and asymmetric stretch modes of the dicarbonyl, followed by much slower (n-hexane, 61 ps; CCl3H, 101 ps) population relaxation. Calculated transient spectra and bleach decay curves obtained from a 5-level density matrix model of the coupled CO oscillators account for the data, including the effects due to perturbed FID and the rapid v-v coupling.
引用
收藏
页码:487 / 497
页数:11
相关论文
共 19 条
[1]  
ANGEL SA, 1990, 7TH P TOP M ULTR PHE
[2]   SUBPICOSECOND TRANSIENT INFRARED-SPECTROSCOPY OF ADSORBATES - VIBRATIONAL DYNAMICS OF CO/PT(111) [J].
BECKERLE, JD ;
CAVANAGH, RR ;
CASASSA, MP ;
HEILWEIL, EJ ;
STEPHENSON, JC .
JOURNAL OF CHEMICAL PHYSICS, 1991, 95 (07) :5403-5418
[3]   TIME-RESOLVED AND STATE-RESOLVED MEASUREMENTS OF NITRIC-OXIDE DIMER INFRARED PHOTODISSOCIATION [J].
CASASSA, MP ;
STEPHENSON, JC ;
KING, DS .
JOURNAL OF CHEMICAL PHYSICS, 1988, 89 (04) :1966-1976
[4]   DYNAMICS OF SPECTRAL HOLE BURNING [J].
CRUZ, CHB ;
GORDON, JP ;
BECKER, PC ;
FORK, RL ;
SHANK, CV .
IEEE JOURNAL OF QUANTUM ELECTRONICS, 1988, 24 (02) :261-266
[5]   SPECTROSCOPIC STUDIES ON ORGANOMETALLIC COMPOUNDS .17. INFRARED SPECTRA OF DICARBONYL-(PI-CYCLOPENTADIENYL)IRON COMPLEXES IN CARBONYL STRETCHING REGIONS [J].
DALTON, J ;
PAUL, I ;
STONE, FGA .
JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1969, (18) :2744-&
[6]   POPULATION LIFETIMES OF OH(V = 1) AND OD(V = 1) STRETCHING VIBRATIONS OF ALCOHOLS AND SILANOLS IN DILUTE-SOLUTION [J].
HEILWEIL, EJ ;
CASASSA, MP ;
CAVANAGH, RR ;
STEPHENSON, JC .
JOURNAL OF CHEMICAL PHYSICS, 1986, 85 (09) :5004-5018
[7]   CO(V=1) POPULATION LIFETIMES OF METAL-CARBONYL CLUSTER COMPOUNDS IN DILUTE CHCL3 SOLUTION [J].
HEILWEIL, EJ ;
CAVANAGH, RR ;
STEPHENSON, JC .
JOURNAL OF CHEMICAL PHYSICS, 1988, 89 (01) :230-239
[9]  
HEILWEIL EJ, 1989, ANNU REV PHYS CHEM, V40, P143
[10]   POPULATION RELAXATION OF CO(V=1) VIBRATIONS IN SOLUTION PHASE METAL-CARBONYL-COMPLEXES [J].
HEILWEIL, EJ ;
CAVANAGH, RR ;
STEPHENSON, JC .
CHEMICAL PHYSICS LETTERS, 1987, 134 (02) :181-188