Erratum: “H2—AgCl: A spectroscopic study of a dihydrogen complex” [J. Chem. Phys. 141, 114306 (2014)] (original) (raw)
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Chemical Physics, 1990
The results of ab initio quantum chemical calculations are reported on the HCl molecule and the hydrogen bonded complexes B...HCl, where B=CO, CzH2, CzH,, PH,, H2S, HCN, Hz0 and NH,. The main emphasis of this work is the accurate calculation of the "Cl nuclear quadrupole coupling constants, using SCF and averaged coupled pair functional methods, accounting for the electrical and geometrical polarization effects as well as librational averaging Other quantities of interest that were calculated and compared with experiment include a range of one-electron properties for the HCl molecule such as its dipole and quadrupole moments, polarixability, the chlorine electric field gradient response tensots as well as derivatives of the field gradient. For the complexes the binding energies, dipole moment shifts, changes in the HCl bond length as well as in its stretching frequency and intensity are also reported. The overall agreement between theory and experiment, where comparison is possible, is very good. The hydrogen bonding and its effects on the dipole moment and the Cl field gradient are also analysed into electrostatic, exchange, polarization and charge transfer contributions using the Morokuma method and the constrained spatial orbital variation approach, these calculations convincingly demonstrate the importance of intermolecular exchange, especially with regard to the Cl field gradient.
An experimental determination of the H2-Ag(110) interaction potential
Surface Science, 1991
An experimental study of the interaction of Hz with the Ag(ll0) surface is presented. The diffractron Intensities. measured at T, = 100 K and corrected by a Debye-Wailer analysis, are analyzed to obtain information on the H,-Ag interaction performing close-coupling calculations for a semi-phenomenological potential which reproduces quite well the experimental data. The comparison between the He-metal and the Hz-metal potentials indicates that the larger corrugation sampled by H, as compared to He. originates from the stronger polarizability of H, Elsevier Science Publishers B.V. (North-Holland) M. Canepa et al. / Determination of the H,-Ag(lI0) interaction potential 1143
Ab Initio Intermolecular Potential of Ar–C2H2 Refined Using High-Resolution Spectroscopic Data
The Journal of Physical Chemistry A, 2013
The high-resolution infrared spectra of the ν 1 + ν 3 (2CH) band of the Ar−C 2 H 2 complex has been recorded from 6544 to 6566 cm −1. The previously reported K a = 1 ← 0, 2 ← 1, and 0 ← 1 subbands were observed and the K a = 1 ← 2, 2 ← 3, and 3 ← 2 subbands were assigned for the first time. The intermolecular potential energy surface of this complex has been calculated ab initio and optimized by fitting the new high-resolution data. Refined intermolecular potential energy surfaces have been obtained for the ground vibrational state and for the excited v 1 = v 3 = 1 stretching state. For the former state, the results of the analysis are satisfactory and the microwave transitions of the complex are reproduced with a root-meansquare deviation of 5 MHz. For the latter state, systematic discrepancies arise in the analysis.
GRECP/RCC calculation of the spectroscopic constants for the HgH molecule and its cation
Generalized relativistic effective core potential (GRECP) calculations of spectroscopic constants of the HgH molecule ground and low excited states and the HgH + cation ground state are carried out, with correlation included by the Fock-space relativistic coupled cluster (RCC) method. Basis set superposition errors (BSSE) are estimated and discussed. It is demonstrated that connected triple excitations of the 13 outermost electrons are necessary to obtain accurate results for mercury hydride. Spectroscopic constants derived from potential curves which include these terms are in very good agreement with experiment, with errors of a few mbohr in R e , tens of wavenumbers in excitation energies and vibrational frequencies, and proportionately for other properties. Comparison with previous calculations is also presented.
The Journal of Physical Chemistry A, 2013
The microwave (4−20 GHz range) and infrared (HCl 10 and DCl stretch ranges) spectra of six isotopic species of the 11 CH 3 Cl−HCl hydrogen bond complex have been recorded for the 12 first time and analyzed with the support of high level ab initio 13 calculations (MP2 and CCSD(T) levels). Accurate molecular 14 parameters, including rotational, quartic centrifugal distortion, and 15 nuclear-quadrupole coupling constants, vibrational frequencies, and 16 anharmonic coupling constants, are presented in this paper. These 17 parameters have then been used to estimate the hydrogen bond 18 geometry and confirm the strong coupling between intramolecular and low frequency intermolecular modes. Experimental and 19 theoretical evidence, in agreement with each other, tend to point out a free rotation of the CH 3 Cl unit in the complex, 20 emphasizing the very peculiar dynamical properties of a hydrogen bond and, consequently, the necessity of taking those effects 21 into account to correctly model the intra-and intermolecular interactions.
Theoretical calculations of the nuclear quadrupole coupling in the spectra of D3+, H2D+, and HD2+
Journal of Molecular Spectroscopy, 1991
The present paper reports a purely theoretical calculation ofthe quadrupole hyperfine structure in the rotation-vibration spectra of D;, HlD', and HD; As the initial step in the calculation we have computed ab initio extensive sets of electric tield gradient values for these molecules. These ab initio values are used. together with rotation-vibration wavefunctions obtained using the rotation-vibration theory developed previously for X, and Y,X equilateral triangular molecules [V. Spirko, P. Jensen, P. R. Bunker, and A. Cejchan, J. Mol. Spectrosc. 112, 183-202 (1985); P. Jensen, V. Spirko, and P. R. Bunker, J. Mol. Spectrosc. 115, 269-293 ( 1986)] to obtain the quadrupole splitting parameters for the individual rotation-vibration states of the molecules in question. We have calculated actual quadrupole splittings for selected transitions of H2D+ and HD; and find these to be less than 100 kHz. Laboratory measurements of these small splittings would require sub-Doppler resolution and do not seem feasible at the present time. Even in cold interstellar clouds HtD+ lines certainly have widths larger than the calculated splittings so that interstellar detection of the splittings is impossible. Clearly in the present study theory is very far ahead of experiment. One might hope that in a not-too-distant future experimental techniques will be developed which allow the observation of the small splittings. cc')
Calculated spectroscopic properties of HgH 2
Molecular Physics, 2007
Ab initio calculations of the coupled cluster and spin-orbit configuration type, in conjunction with a small-core pseudopotential for the mercury atom, have been employed to construct near-equilibrium potential energy and electric dipole moment functions for HgH 2 . On that basis, rovibrational term energies and wavefunctions as well as transition dipole moments, absolute IR intensities and Einstein coefficients of spontaneous emission have been calculated variationally. Throughout, excellent agreement is obtained with recent experimental data from Fourier-transform infrared emission spectroscopy (A. Shayesteh, S. Yu , P. F. Bernath, J. Phys. ).
GRECP/RCC-SD calculation of the spectroscopic constants for the HgH molecule and its ions
Generalized Relativistic Effective Core Potential (GRECP) calculation of spectroscopic constants for the HgH molecule and its ions is carried out with the help of Fock-space Relativistic Coupled Cluster method with Single and Double cluster amplitudes (RCC-SD). The calculated spectroscopic constants are compared with experimental data and results of calculations of other groups. Errors of the performed GRECP/RCC-SD calculations are analyzed. The Basis Set Superposition Errors (BSSE) are estimated and discussed.
Ab Initio Molecular Orbital Computation Studies of Ag+-C2H4 Complexation in the Presence of Water
Ab initio calculations are done to explore the influence of water on the Ag + -C 2 H 4 complex formation. The simulated coordination environment of Ag ion is based on the existence of a dynamic equilibrium between the coordination of Ag ion with water and a sulfonate group, the counter ion. Calculated electronic properties reveal that electron delocalization from water molecules and the sulfonate group onto Ag 5s-atomic orbital reduces the ability of Ag ion to accept additional electrons from the C 2 H 4 π-orbital. The dissociation of water molecules from the hydrated Ag + is essential for the thermodynamic possibility of the Ag-C 2 H 4 complex formation. It is also evident from the electronic structure calculations that the dissociation of water is favorable for the formation of a stable Ag-C 2 H 4 complex. In the absence of water, the reaction between Ag ion strongly bound to sulfonate group and C 2 H 4 is thermodynamically impossible.
Direct-potential-fit analysis of new infrared and UV/visible A Σ-X Σ emission spectra of AgH and AgD
The Journal of chemical …, 2005
New high-resolution infrared and UV/visible spectra of 107 AgH, 109 AgH, 107 AgD, and 109 AgD have been recorded with a Fourier transform spectrometer. The new line positions are combined with published microwave and older electronic A 1 ⌺ + -X 1 ⌺ + data and used, first in a decoupled analysis of the X state alone, and then in a global multi-isotopologue analysis which yields comprehensive descriptions of both the X 1 ⌺ + and A 1 ⌺ + states of all four isotopologues of AgH. While the A state was long believed to be heavily perturbed, it is shown that its irregular spectrum merely reflects an unusual potential function shape. A direct fit of all data to appropriate radial Hamiltonians yields analytic potential-energy functions and Born-Oppenheimer breakdown radial functions for the ground X 1 ⌺ + and A 1 ⌺ + states.