Search results for "PERTURBATION"
showing 10 items of 811 documents
Extrapolation of water and formaldehyde harmonic and anharmonic frequencies to the B3LYP/CBS limit using polarization consistent basis sets
2010
The harmonic and anharmonic frequencies of fundamental vibrations in formaldehyde and water were successfully estimated using the B3LYP Kohn-Sham limit. The results obtained with polarization- and correlation-consistent basis sets were fitted with a two-parameter formula. Anharmonic corrections were obtained by a second order perturbation treatment (PT2). We compared the performance of the PT2 scheme on the two title molecules using SCF, MP2 and DFT (BLYP, B3LYP, PBE and B3PW91 functionals) methods combined with polarization consistent pc-n (n = 0, 1, 2, 3, 4) basis sets, Dunning’s basis sets (aug)-cc-pVXZ where X = D, T, Q, 5, 6 and Pople’s basis sets up to 6-311++G(3df,2pd). The influence…
Numerical stochastic perturbation theory in the Schrödinger functional
2013
The Schr\"odinger functional (SF) is a powerful and widely used tool for the treatment of a variety of problems in renormalization and related areas. Albeit offering many conceptual advantages, one major downside of the SF scheme is the fact that perturbative calculations quickly become cumbersome with the inclusion of higher orders in the gauge coupling and hence the use of an automated perturbation theory framework is desirable. We present the implementation of the SF in numerical stochastic perturbation theory (NSPT) and compare first results for the running coupling at two loops in pure SU(3) Yang-Mills theory with the literature.
A theoretical study of the collinear reaction F+H2→HF+H using multiconfigurational second-order perturbation theory (CASPT2)
1993
Abstract The second-order perturbation method (CASPT2) with a single state multiconfigurational reference function generated in complete active self-consistent field (CASSCF) calculations has been used to compute the collinear barrier height, saddle point geometry, and exothermicity of the reaction F+H 2 →HF+H. Comparison with full configuration (FCI) calculations with small basis sets shows that the CASPT2 method is capable of reproducing accurately the exact benchmark results correlating seven electrons. Large atomic natural orbital basis sets are used at the seven- and nine-electron level of correlation. With the largest ANO basis set used, F[7s6p5d4f2g]/H[6s5p4d2f], the computed nine-el…
Quantum chemistry of the excited state: 2005 overview
2005
The present contribution contains an overview of quantum-chemical methods and strategies to compute and interpret spectroscopic and photochemical phenomena in molecular systems. The state of the art for the quantum chemistry of the excited state is reviewed, focusing in the advantages and disadvantages of the most commonly employed computational methods, from the single configurational procedures like CI-Singles (CIS), propagator approaches, and Coupled-Cluster (CC) techniques, to the more sophisticated multiconfigurational treatments, with particular emphasis on perturbation theory, the CASPT2 approach. Also, a short summary on the performance, lights, and shadows of the popular TDDFT meth…
Nonlinear response theory for Markov processes: simple models for glassy relaxation.
2012
The theory of nonlinear response for Markov processes obeying a master equation is formulated in terms of time-dependent perturbation theory for the Green's functions and general expressions for the response functions up to third order in the external field are given. The nonlinear response is calculated for a model of dipole reorientations in an asymmetric double well potential, a standard model in the field of dielectric spectroscopy. The static nonlinear response is finite with the exception of a certain temperature $T_0$ determined by the value of the asymmetry. In a narrow temperature range around $T_0$, the modulus of the frequency-dependent cubic response shows a peak at a frequency …
Domains of Convergence of Kam Type Iterations for Eigenvalue Problems
1999
The KAM technique was first introduced to deal with small denominator problems appearing in perturbation of invariant tori in classical mechanics [1, 2]. Similar methods were later applied to many different problems, like e.g. eigenvalue problems for time dependent problems in the Floquet representation [3, 4, 5, 6]. Most of the known results are valid for sufficiently small perturbation of some simple (integrable) system. The phenomena arising for large perturbations, in particular critical perturbations at which a given torus loses its stability, have been discussed in the framework of some approximate schemes inspired in renormalization group ideas [7, 8, 9]. In this framework, an iterat…
Two-laser multiphoton adiabatic passage in the frame of the Floquet theory. Applications to (1+1) and (2+1) STIRAP
1998
We develop an adiabatic two-mode Floquet theory to analyse multiphoton coherent population transfer in N-level systems by two delayed laser pulses, which is a generalization of the three-state stimulated Raman adiabatic passage (STIRAP). The main point is that, under conditions of non-crossing and adiabaticity, the outcome and feasibility of a STIRAP process can be determined by the analysis of two features: (i) the lifting of degeneracy of dressed states at the beginning and at the end of the laser pulses, and (ii) the connectivity of these degeneracy-lifted branches in the quasienergy diagram. Both features can be determined by stationnary perturbation theory in the Floquet representation…
Reverse and normal drag along a fault
2005
An analysis of the theoretical displacement field around a single dip-slip fault at depth reveals that normal and reverse fault drag develop by perturbation flow induced by fault slip. We analytically model the heterogeneous part of the instantaneous displacement field of an isolated two-dimensional mode II fault in an infinite, homogeneous elastic body in response to fault slip. Material on both sides of the fault is displaced and ‘opposing circulation cells’ arise on opposite sides of the fault, with displacement magnitudes increasing towards the center of the fault. Both normal and reverse drag can develop at the fault center depending on the angle between the markers and the fault; norm…
Stochastic resonance in a trapping overdamped monostable system.
2009
The response of a trapping overdamped monostable system to a harmonic perturbation is analyzed, in the context of stochastic resonance phenomenon. We consider the dynamics of a Brownian particle moving in a piecewise linear potential with a white Gaussian noise source. Based on linear-response theory and Laplace transform technique, analytical expressions of signal-to-noise ratio (SNR) and signal power amplification (SPA) are obtained. We find that the SNR is a nonmonotonic function of the noise intensity, while the SPA is monotonic. Theoretical results are compared with numerical simulations.
Applications of level shift corrected perturbation theory in electronic spectroscopy
1996
Abstract Multiconfigurational second-order perturbation theory (CASPT2) with a level shift technique used to reduce the effect of intruder states has been tested for applications in electronic spectroscopy. The following molecules have been studied: formamide, adenine, stilbene, Ni(CO) 4 , and a model compound for the active site in the blue copper protein plastocyanin, Cu(Im) 2 (SH)(SH 2 ) + . The results show that the level shift technique can be used to remove the effects of the intruder states in all these molecules. In some cases a drift in the energies as a function of the level shift is observed, which however is small enough that the normal error bar for CASPT2 excitation energies (…