Vibrational corrections to electric properties of relativistic molecules: The coinage metal hydrides

Abstract

Articles you may be interested inDynamic (hyper)polarizabilities of the ozone molecule: Coupled cluster calculations including vibrational corrections J. Chem. Phys. 134, 054315 (2011); 10.1063/1.3552072Theoretical study of the X Σ 2 + states of the neutral CM-RG complexes ( CM = coinage metal, Cu, Ag, and Au and RG = rare gas, He-Rn) Molecular density functional calculations in the regular relativistic approximation: Method, application to coinage metal diatomics, hydrides, fluorides and chlorides, and comparison with first-order relativistic calculationsThe dipole moment, parallel dipole polarizability, and the parallel first hyperpolarizability of the coinage metal hydrides ͑CuH, AgH, AuH͒ are studied in the context of their vibrational contributions. The partition of the property values into pure electronic, vibrational averaging, and pure vibrational terms is discussed, and the corresponding contributions are calculated by means of the field-dependent Numerov-Cooley integration technique. The potential energy and property surfaces, required for the evaluation of these contributions, follow from different high-level electronic structure calculations. Parallel to the nonrelativistic studies, a relativistic treatment of the investigated properties has been carried out. It has been found that relativistic effects significantly reduce the magnitude of the vibrational corrections to the studied properties. A particularly large relativistic reduction has been found for the vibrational contribution to the first hyperpolarizability. The relativistic effect is enhanced with increasing nuclear charge of the heavy atom, and can be interpreted in terms of the relativistic effect on the potential energy and electric property curves.

Theoretical investigation of structures, electronic spectra and nonlinear optical properties of gold-pentacene (Au2C22H14) complexes

“…Recent study shows that organometallic complexes offer greater scope for creation of multifunctional NLO materials by virtue of their greater design flexibility and low energy, yet sometimes intense electronic transitions [17][18][19][20][21][22][23]. Moreover, a series of experimental [24][25][26][27] and theoretical investigations [28][29][30][31][32][33] on NLO properties of gold complexes and gold clusters have been done. These complexes have already exhibited excellent NLO response.…”

Probing the structural and electronic properties of AgnH− (n = 1–3) using photoelectron imaging and theoretical calculations

“…Hydride clusters of Group IB metals have been good prototypes to understand the influences of this important effect. [1][2][3][4][5] To understand the adsorption of hydrogen atom on the silver surfaces and to elucidate the origin of unusual chemical activities of small silver particles, silver hydride clusters have attracted great interests for a long time. [6][7][8][9][10][11] As the simplest silver hydride system, AgH has been well studied using spectroscopic and theoretical methods long ago.…”

Basis set and electron correlation effects on initial convergence for vibrational nonlinear optical properties of conjugated organic molecules

“…[1][2][3][4][5][6][7][8] Due to the high computational cost, electron correlation has rarely been included in ab initio calculations of the vibrational hyperpolarizability of medium size or large NLO organic molecules. In the few studies available, only the harmonic terms ͑i.e., double harmonic approximation͒ 1,6,9 or the lowest order anharmonic terms ͑i.e., nuclear relaxation contribution, ␤ nr and ␥ nr ) [10][11][12] were computed.…”