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Full-Text Articles in Chemistry

Femtosecond Nuclear Motion Of Hcl Probed By Resonant X-Ray Raman Scattering In The Cl 1s Region, Marc Simon, Loic Journel, Stephane Carniato, Richard Taieb, I. Minkov, Faris Gel'mukhanov, P. Salek, H. Agren, Renaud Guillemin, Wayne C. Stolte, A. C. Hudson, Dennis W. Lindle Feb 2006

Femtosecond Nuclear Motion Of Hcl Probed By Resonant X-Ray Raman Scattering In The Cl 1s Region, Marc Simon, Loic Journel, Stephane Carniato, Richard Taieb, I. Minkov, Faris Gel'mukhanov, P. Salek, H. Agren, Renaud Guillemin, Wayne C. Stolte, A. C. Hudson, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Femtosecond dynamics are observed by resonant x-ray Raman scattering (RXS) after excitation along the dissociative Cl 1s→6ơ* resonance of gas-phase HCl. The short core-hole lifetime results in a complete breakdown of the common nondispersive behavior of soft-x-ray transitions between parallel potentials. We evidence a general phenomenon of RXS in the hard-x-ray region: a complete quenching of vibrational broadening. This opens up a unique opportunity for superhigh resolution x-ray spectroscopy beyond vibrational and lifetime limitations.


Population Size Bias In Descendant-Weighted Diffusion Quantum Monte Carlo Simulations, G. Lee Warren, Robert J. Hinde Jan 2006

Population Size Bias In Descendant-Weighted Diffusion Quantum Monte Carlo Simulations, G. Lee Warren, Robert J. Hinde

Chemistry Publications and Other Works

We consider the influence of population size on the accuracy of diffusion quantum Monte Carlo simulations that employ descendant weighting or forward walking techniques to compute expectation values of observables that do not commute with the Hamiltonian. We show that for a simple model system, the d-dimensional isotropic harmonic oscillator, the population size must increase rapidly with d in order to ensure that the simulations produce accurate results. When the population size is too small, expectation values computed using descendant-weighted diffusion quantum Monte Carlo simulations exhibit significant systematic biases.


Interaction-Induced Dipole Moment Of The Ar–H2 Dimer: Dependence On The H2 Bond Length, Robert J. Hinde Jan 2006

Interaction-Induced Dipole Moment Of The Ar–H2 Dimer: Dependence On The H2 Bond Length, Robert J. Hinde

Chemistry Publications and Other Works

We present ab initio calculations of the interaction-induced dipole moment of the Ar–H2 van der Waals dimer. The primary focus of our calculations is on the H2 bond length dependence of the dipole moment, which determines the intensities of both the collision-induced H2 = 1 ← 0 fundamental band in gaseous Ar–H2 mixtures and the dopant-induced H2 = 1 ← 0 absorption feature in Ar-doped solid H2 matrices. Our calculations employ large atom-centered basis sets, diffuse bond functions positioned between the two monomers, and a coupled cluster treatment of valence electron correlation; core-valence correlation …


Interaction-Induced Dipole Moment Of The Ar–H2 Dimer: Dependence On The H2 Bond Length, Robert J. Hinde Jan 2006

Interaction-Induced Dipole Moment Of The Ar–H2 Dimer: Dependence On The H2 Bond Length, Robert J. Hinde

Robert Hinde

We present ab initio calculations of the interaction-induced dipole moment of the Ar–H2 van der Waals dimer. The primary focus of our calculations is on the H2 bond length dependence of the dipole moment, which determines the intensities of both the collision-induced H2 = 1 ← 0 fundamental band in gaseous Ar–H2 mixtures and the dopant-induced H2 = 1 ← 0 absorption feature in Ar-doped solid H2 matrices. Our calculations employ large atom-centered basis sets, diffuse bond functions positioned between the two monomers, and a coupled cluster treatment of valence electron correlation; core-valence correlation …


Population Size Bias In Descendant-Weighted Diffusion Quantum Monte Carlo Simulations, G. Lee Warren, Robert Hinde Jan 2006

Population Size Bias In Descendant-Weighted Diffusion Quantum Monte Carlo Simulations, G. Lee Warren, Robert Hinde

Robert Hinde

We consider the influence of population size on the accuracy of diffusion quantum Monte Carlo simulations that employ descendant weighting or forward walking techniques to compute expectation values of observables that do not commute with the Hamiltonian. We show that for a simple model system, the d-dimensional isotropic harmonic oscillator, the population size must increase rapidly with d in order to ensure that the simulations produce accurate results. When the population size is too small, expectation values computed using descendant-weighted diffusion quantum Monte Carlo simulations exhibit significant systematic biases.