Diabatic analysis of the electronic states of hydrogen chloride (original) (raw)
Related papers
The Journal of Physical Chemistry, 1989
The dissociative excitation of HCI in collision with He(23Sl), He(23SI) + HC1(XIZ+)-He(l'So) + C1(2P) + H*(n>2), is investigated by performing an SCF-CI calculation of the potential energy hypersurfaces relevant to this reaction. The most likely transient excited states of HCI are found to be the dissociative Rydberg states, 222+-As and 1411-4p, which have doubly excited configurations, (3pt)-z(3pa*)'(4s)' and (3p~)-'(3pt)-~(3pa*)'(4p)', respectively. Mechanisms of the formation of these doubly excited states are studied. It is found that the formation of the 22Z+-4s state is induced by mixing of the inner valence hole configuration, (3sa)-'(4s)', into the 2%+-4s state, while the 1411-4p state is produced by mixing of a charge-transfer configuration, He+ + HCl-, with He(2%') + HCl and He + HC1(1411-4p) as initial and final states, respectively.
The Journal of Chemical Physics, 1995
The fine structure branching ratio of chlorine atoms produced in the photodissociation and predissociation of HCl was measured for excitation energies between 51 800 and 83 800 cm Ϫ1 . The branching ratio between 60 000 and 70 000 cm Ϫ1 is in good agreement with the calculations of Alexander et al. ͓J. Chem. Phys. 99, 1752 ͑1993͔͒, converging to the statistical limit at high energy. Predissociation of electronically excited bound states display a surprisingly rich behavior, demonstrating that the nature of the predissociating continuum state has a large effect on the atom fragment branching ratio.
Spin-Orbit Coupling , Spin-Spin , NMR and Electric Properties of Hydrogen Chloride Molecule
2014
Research includes the study of the spin-orbit coupling, spin-spin, NMR, electronic structure and number electric properties such as ionization potential(IP), electron affinity(EA), electronegativity (x), hardness(), softness(S), electrophilic(W) and NMR spectroscopy of hydrogen chloride molecule by using Gaussian program 09 and Gauss view 5.08 program using density function (DFT) method B3LYP/6-311G (d,p).
International Journal of Quantum Chemistry, 2011
Starting with the Hamilton-Jacobi equation, Campos et al. have applied Hylleraas' method along with the series obtained by Wind-Jaffe to several molecular ions, among which the H + 2 system, to determine their electronic energies in different states. In this work, we have fitted the potential energy curves for the 2pπ, 3dσ , 4dσ , 4f π, 4f σ , 5gσ , and 6iσ electronic states of the H + 2 ion employing the Rydberg generalized function. From these fittings, the spectroscopic constants and the rovibrational energies have been determined by two distinct methods: Dunham's and the discrete variable representation. The theoretically obtained results are in a satisfactory agreement and are expected to provide a comparison source to future works in the experimental field.
Potential curves and predissociation rates for the species HCl2+ and DCl2+
Chemical Physics, 1988
Potential energy curves for all HCl* + states which correlate with the first five dis~ciation limits are calculated emplo~ng multireference con~~~tion-interaction (MRD CI) treatments in a Gaussian A0 basis containing up to four d and one f function for chlorine and two p functions for hydrogen. Tunneling rates for the X '2?, a 'A and b 'I? vibrational levels in HCIZ+ and DC]*+ are calculated as well as predissociation rates for vibrational levels of the a 'A and b 'F' states due to spin-orbit interaction with the 'II state. The spin-orbit coupling elements are evaluated explicitly by employing the Breit-Pauli operator and the MRD CI wavefunctions. Comparison with previous works is given.
Journal of Molecular Spectroscopy, 2017
Mass resolved resonance enhanced multiphoton ionization (REMPI) spectra of a mixture of DCl and HCl were recorded for two-photon resonance excitation in the region of 80 500-89 500 cm À1. Spectra due to resonance transitions to rovibrational states of number of Rydberg and ion-pair states of DCl, were identified and assigned. Five new spectral bands due to transitions to Rydberg states and eight new bands due to transitions to vibrational states of the ion-pair state were identified and analysed to derive energetic parameters. Irregularities observed in vibrational energy level spacing, rotational constants and isotope shifts of chlorine isotopologues from what to expect for unperturbed states, as well as relative signal intensities, are indicative of strong homogeneous interaction between the E 1 R + Rydberg state and the V 1 R + ion-pair state. These observations are found to be due to level-to-level interaction between E and V rovibrational states of same J 0 quantum numbers. Comparison of the data for DCl and HCl is performed.
Chinese Journal of Chemical Physics, 2021
We report full-dimensional and fully coupled quantum bound-state calculations of the J=1 intra-and intermolecular rovibrational states of two isotopologues of the hydrogen chloride-water dimer, HCl-H 2 O (HH) and DCl-H 2 O (DH). The present study complements our recent theoretical investigations of the J=0 nine-dimensional (9D) vibrational level structure of these and two other H/D isotopologues of this noncovalently bound molecular complex, and employs the same accurate 9D permutation invariant polynomial-neural network potential energy surface. The calculations yield all intramolecular vibrational fundamentals of the HH and DH dimers and the low-energy intermolecular rovibrational states in these intramolecular vibrational manifolds. The results are compared with those of the 9D J=0 calculations of the same dimers. The energy differences between the K=1 and K=0 eigenstates exhibit pronounced variations with the intermolecular rovibrational states, for which a qualitative explanation is provided.
Multiphoton Ionization and Fragmentation of Hydrogen Chloride: A Diatomic Still Good for a Surprise
Journal of Atomic, Molecular, and Optical Physics, 2011
The competition between multiphoton ionization and fragmentation in the diatomic molecule hydrogen chloride is reviewed. Emphasis is laid on recent experimental results employing chemical imaging methods in order to obtain kinetic energy distributions and angular distributions of photoproducts. The energy range considered is 15 to 20 eV, equivalent to the absorption of three or four photons in the ultraviolet wavelength range. The role of Rydberg states as resonantly excited intermediate states in the ionization/fragmentation processes is assessed. Mixing among 1 Σ + states gives rise to peculiarly shaped double minimum potential energy curves which allow for the production of hydrogen and chlorine atomic and ionic fragments via several competing pathways, in addition to the production of molecular HCl + ions. States with different electronic properties show a qualitatively different behaviour from Σ + states. Accidental resonances between states of differing orbital angular momentum or multiplicity serve to override these differences and cause subtle as well as significant deviations from the unperturbed behaviour.
The Predissociation Mechanism for2Σ+Rydberg States of CaCl
Journal of Molecular Spectroscopy, 1999
This work summarizes experimental results from recent ion-dip spectroscopy studies of CaCl and from previously unpublished optical-optical double-resonance work with specific regard to predissociation processes of 2 ⌺ ϩ Rydberg states in the low n* (n* ϭ 7, IP Ϫ E n* ϭ 2240 cm Ϫ1 ) region. A single repulsive state (assigned as 2 ⌺ ϩ ) was found to be responsible for all observed predissociations of 2 ⌺ ϩ Rydberg states. The n*-dependent internuclear distances of the intersections between Rydberg states and the repulsive 2 ⌺ ϩ state were determined through the use of trial-and-error Franck-Condon calculations. Values of energy-descaled electronic matrix elements governing the Rydberg 7 repulsive state interaction were obtained from the measured linewidths (0.6 Ͻ ⌫ Ͻ 1.2 cm Ϫ1 ) and computed Franck-Condon densities.
Photodissociation of HCl at 193.3 nm: Spin–orbit branching ratio
The Journal of Chemical Physics, 1997
HCl was photodissociated by ultraviolet ͑uv͒ radiation at 193.3 nm. Time-of-flight spectra of the hydrogen atom fragment provided the spin-orbit state distribution of the chlorine fragment, ͓Cl(2 P 1/2)͔/͓Cl(2 P 3/2)͔ϭ0.69Ϯ0.02, in excellent agreement with recent theoretical studies. The H atom angular distribution studied by changing the uv photolysis laser polarization confirmed a dominant A 1 ⌸←X 1 ⌺ ϩ electronic transition in the photoexcitation process ͑ϭϪ1.01Ϯ0.04 and *ϭϪ0.94Ϯ0.07͒.