Infrared spectroscopic studies of the rare gas atom perturbed S1(0) rovibron band of solid parahydrogen

Anderson, David T.

doi:10.1016/j.jms.2007.05.014

Cited by 7 publications

(5 citation statements)

References 40 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The Br 2 concentration can also be monitored by examining the Q 1 (0) induced region. 38,41,42 Representative spectra in the Q 1 (0) induced region (B4150 cm À1 ) are shown on the right side of Fig. 3.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and infrared characterization of Br–HBr and Br–DBr entrance channel complexes in solid parahydrogen

Kettwich

Pinelo

Anderson

2008

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

We report high resolution vibrational spectra in the HBr (2560 cm(-1)) and DBr (1840 cm(-1)) stretching regions for Br-HBr and Br-DBr entrance channel complexes isolated in solid parahydrogen (pH2). The Br-HBr complexes are generated by synthesizing solid pH2 crystals doped with trace amounts of HBr/Br2 mixtures followed by 355 nm in situ photodissociation of Br2 to form Br atoms. After photolysis is complete, the solid is warmed from 2 to 4.3 K resulting in the irreversible formation of Br-HBr complexes. The large 36.63 cm(-1) HBr monomer-to-complex induced vibrational shift to lower energy measured in these studies is consistent with the linear Br-HBr hydrogen bonded structure predicted from theory. The 0.02 cm(-1) Br-HBr absorption linewidths indicate a 1 ns vibrational excited state lifetime for these entrance channel complexes in solid pH2.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis and infrared characterization of Br–HBr and Br–DBr entrance channel complexes in solid parahydrogen

Kettwich

Pinelo

Anderson

2008

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

show abstract

“…More recently, a number of researchers have started using SMH as a host for IR matrix isolation spectroscopy. , The addition of a low concentrations of dopant species induces new IR absorption features in the SMH host due to dopant-host intermolecular interactions. − In principle, the frequencies and intensities of these dopant induced features contain information about the SMH host in the immediate vicinity of the dopant. Similar to the induced absorption features in neat SMH, the dopant induced features are created by pairwise interactions between the dopant and H 2 host.…”

Section: Introductionmentioning

confidence: 99%

“…This begs the question, are the FA-induced nH 2 absorptions different for trans -HCOOH and cis -HCOOH? The understanding of dopant induced SMH features is well developed for atoms and diatomic molecules; − however, more work is needed to understand the induced features produced by larger dopant molecules such as FA. The motivation for developing this theoretical framework is that by their very nature the dopant induced H 2 features have encoded in their IR spectrum information about the geometry and dynamics of the dopant solvation site, and thus a well-developed theoretical understanding could lead to a new spectroscopic probe of solvation in SMH.…”

Section: Introductionmentioning

confidence: 99%

Conformation Resolved Induced Infrared Activity: trans- and cis-Formic Acid Isolated in Solid Molecular Hydrogen

et al. 2011

Self Cite

View full text Add to dashboard Cite

We report combined experimental and theoretical studies of infrared absorptions induced in solid molecular hydrogen by different conformers of formic acid (HCOOH, FA). FTIR spectra recorded in the H(2) fundamental region (4120-4160 cm(-1)) reveal a number of relatively strong trans-FA induced Q-branch absorptions that are assigned by studying both FA-doped parahydrogen (pH(2)) and normal hydrogen (nH(2)) samples. The induced H(2) absorptions are also studied for HCOOD doped nH(2) crystals for both the trans and cis conformers that show resolvable differences. Samples containing >90% of the higher energy cis-HCOOD conformer are produced by in situ IR pumping of the OD stretching overtone of trans-HCOOD using narrow-band IR light. Minimum energy structures for 1:1 complexes of H(2) and FA are determined using ab initio methods. The measured differences in the cis- versus trans-HCOOD induced spectra are in qualitative agreement with the frequencies and intensities calculated for the identified cluster structures as discussed in terms of the model of specific interactions.

show abstract

“…On the other hand, if the pH 2 molecule undergoing the S 1 (0) transition is in a locally fcc-like region of the solid, the dipole moments induced in its pH 2 neighbors sum to zero, and the transition is electric dipole forbidden. 30,31 Exactly the same induction mechanism should apply to the 2 P 1/2 ← 2 P 3/2 SO transition of halogen atoms trapped in solid pH 2 . The only difference is that in this case, the excitation destroys the quadrupolar electric field that is responsible for inducing dipole moments in nearby pH 2 molecules.…”

Section: So Transition Intensities For Ph 2 -Trapped Halogen Atomsmentioning

confidence: 94%

Infrared-active spin-orbit transitions of halogen atom dopants in solid parahydrogen: The role of trapping site geometry

Hinde

2013

The Journal of Chemical Physics

View full text Add to dashboard Cite

We present theoretical calculations of the (2)P(1/2) ← (2)P(3/2) spin-orbit transition of Cl dopants embedded as substitutional impurities in solid parahydrogen (pH2) matrices. In the lower-energy (2)P(3/2) spin-orbit level, the Cl atom's electron density distribution is anisotropic, and slightly distorts the geometry of the atom's trapping site. This distortion leads to a blue shift in the spin-orbit transition energy; the blue shift is enhanced when we account for the large-amplitude zero point motions of the pH2 molecules surrounding the Cl dopant. We also show that the intensity of the transition depends on the geometry of the trapping site. In the gas phase, the (2)P(1/2) ← (2)P(3/2) atomic transition is electric dipole forbidden. However, when the Cl atom resides in trapping sites that mimic the hexagonal close packed morphology of pure solid pH2, the transition becomes electric dipole allowed through interaction-induced transition dipole moments. These transition dipole moments originate in the anisotropic electron density distribution of the lower-energy (2)P(3/2) spin-orbit level.

show abstract

Infrared spectroscopic studies of the rare gas atom perturbed S1(0) rovibron band of solid parahydrogen

Cited by 7 publications

References 40 publications

Synthesis and infrared characterization of Br–HBr and Br–DBr entrance channel complexes in solid parahydrogen

Synthesis and infrared characterization of Br–HBr and Br–DBr entrance channel complexes in solid parahydrogen

Conformation Resolved Induced Infrared Activity: trans- and cis-Formic Acid Isolated in Solid Molecular Hydrogen

Infrared-active spin-orbit transitions of halogen atom dopants in solid parahydrogen: The role of trapping site geometry

Contact Info

Product

Resources

About