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In this paper, we present a new approach to treat the electronic structure of a molecule in solution. Unlike the hybrid-type method, such as the reference interaction site model self-consistent-field theory, the new approach describes not only the electronic structure of solute but also solute–solvent interactions in terms of the quantum chemistry based on the Hartree–Fock frozen density formulation. In the treatment, the quantum effect due to solvent, including exchange repulsion, is projected on to the solute Hamiltonian using the spectral representation method. The solvent distribution around the solute is handled by the integral equation theory of liquids. As illustrative applications of the approach, the electronic and solvation structure of noble atoms, neon and argon, in liquid neon are studied. We also investigate the electronic structure of an excess electron in liquid helium. The preliminary results demonstrate that the quantum-mechanical effect on the electronic and solvation structure of the solute due to solvent molecules is successfully represented by the new method.In this paper, we present a new approach to treat the electronic structure of a molecule in solution. Unlike the hybrid-type method, such as the reference interaction site model self-consistent-field theory, the new approach describes not only the electronic structure of solute but also solute–solvent interactions in terms of the quantum chemistry based on the Hartree–Fock frozen density formulation. In the treatment, the quantum effect due to solvent, including exchange repulsion, is projected on to the solute Hamiltonian using the spectral representation method. The solvent distribution around the solute is handled by the integral equation theory of liquids. As illustrative applications of the approach, the electronic and solvation structure of noble atoms, neon and argon, in liquid neon are studied. We also investigate the electronic structure of an excess electron in liquid helium. The preliminary results demonstrate that the quantum-mechanical effect on the electronic and solvation structure of the s...

We continue to study exponential ansatz as a candidate of the structure of the exact wave function. We divide the Hamiltonian into ND (number of divisions) parts and extend the concept of the coupled cluster (CC) theory such that the cluster operator is made of the divided Hamiltonian. This is called extended coupled cluster (ECC) including ND variables (ECCND). It is shown that the S(simplest)ECC, including only one variable (ND=1), is exact in the sense that it gives an explicit solution of the Schrodinger equation when its single variable is optimized by the variational or H-nijou method. This fact further implies that the ECCND wave function with ND⩾2 should also have a freedom of the exact wave function. Therefore, by applying either the variational equation or the H-nijou equation, ECCND would give the exact wave function. Though these two methods give different expressions, the difference between them should vanish for the exact wave function. This fact solves the noncommuting problem raised in Paper I [H. Nakatsuji, J. Chem. Phys. 113, 2949 (2000)]. Further, ECCND may give more rapidly converging solution than SECC because of its non-linear character, ECCND may give the exact wave function at the sets of variables different from SECC. Thus, ECCND is exact not only for ND=1, but also for ND⩾2. The operator of the ECC, exp(S), is an explicit expression of the wave operator that transforms a reference function into the exact wave function. The coupled cluster including general singles and doubles (CCGSD) proposed in Paper I is an important special case of the ECCND. We have summarized the method of solution for the SECC and ECCND truncated at order n. The performance of SECC and ECC2 is examined for a simple example of harmonic oscillator and the convergence to the exact wave function is confirmed for both cases. Quite a rapid convergence of ECC2 encourages an application of the ECCND to more general realistic cases.

In this paper we present the quasi-Gaussian entropy theory in a comprehensive and consistent way, introducing a new derivation of the theory very suited for applications to molecular systems, and addressing its use in the case of multi-phase systems. A general derivation of the possible confinement of the system within a part of phase space is given, and for water it is shown that for this a hard sphere excluded volume model can be used. To obtain the temperature dependence of the pressure, a new differential equation is derived, and besides the previously introduced Gaussian and Gamma states, in this paper we also describe a new statistical state, the Inverse Gaussian state. We discuss the properties of these different statistical states and for water compare their thermodynamics with experimental data, finding that both the Gamma and Inverse Gaussian states are excellent descriptions. (C) 1997 American Institute of Physics.

This paper presents a detailed study of a water adlayer adsorbed on Pt(111) and Rh(111) surfaces using periodic density functional theory methods. The interaction between the metal surface and the water molecules is assessed from molecular dynamics simulation data and single point electronic structure calculations of selected configurations. It is argued that the electron bands around the Fermi level of the metal substrate extend over the water adlayer. As a consequence in the presence of the water layer the surface as a whole still maintains its metallic conductivity-a result of a crucial importance for understanding the process of electron transfer through the water/metal interface and electrochemical reactions in particular. Our results also indicate that there exists a weak bond between the hydrogen of the water and the Rh metal atoms as opposed to the widespread (classical) models based on purely repulsive interaction. This suggests that the commonly used classical interactions potentials adopted for large scale molecular dynamics simulations of water/metal interfaces may need revision. Two adsorption models of water on transition metals with the OH bonds pointing towards or away of the surface are also examined. It is shown that due to the very close values of their adsorption energies one should consider the real structure of water on the surface as a mixture of these simple "up" and "down" models. A model for the structure of the adsorbed water layer on Rh(111) is proposed in terms of statistical averages from molecular dynamics simulations.

Quasirelativistic theory of magnetic shielding constants based on the Douglas–Kroll–Hess transformation of the magnetic potential presented in a previous paper is extended to molecular systems that contain heavy elements. The gauge-including atomic orbital method is adapted to the quasirelativistic Hamiltonian to allow origin-independent calculations. The present theory is applied to the proton and halogen magnetic shielding constants of hydrogen halides and the 199Hg magnetic shielding constants and chemical shifts of mercury dihalides and methyl mercury halides. While the relativistic correction to the magnetic interaction term has little effect on the proton magnetic shielding constants, this correction is a dominant origin of the heavy atom shifts of the magnetic shielding constants of heavy halogens and mercury. The basis set-dependence of mercury shielding constants is quite large in the relativistic calculation; it is important to use the basis functions that are optimized by the relativistic metho...

In molecular J-aggregates one often observes an increase of the fluorescence decay time when increasing the temperature from 0 K. This phenomenon is usually attributed to the thermal population of the dark Frenkel exciton states that lie above the superradiant bottom state of the exciton band. In this paper, we study this effect for a homogeneous one-dimensional aggregate in a host medium and we model the scattering between different exciton states as arising from their coupling to the host vibrations. A Pauli master equation is used to describe the redistribution of excitons over the band. The rates entering this equation are calculated within the framework of first-order perturbation theory, assuming a linear on-site interaction between excitons and acoustic phonons. Solving the master equation numerically for aggregates of up to 100 molecules, we calculate the temperature dependence of the fluorescence kinetics in general and the decay time scale in particular. The proper definition of the fluorescence decay time is discussed in detail. We demonstrate that, even at a quantum yield of unity, the possibility to directly interpret fluorescence experiments in terms of a simple radiative time scale depends crucially on the initial excitation conditions in combination with the competition between spontaneous emission and intraband phonon-assisted relaxation.

Self-consistent field (SCF) theory is used to find bending moduli of surfactant and lipid bilayers. Recently, we successfully applied low-memory search methods to solve the SCF equations. Using these we are now able to directly evaluate the Gaussian bending modulus for molecularly detailed models of bilayers by evaluating the excess Helmholtz energy of tensionless bilayers in a (part of the) Im3m cubic phase. The result prompted us to reconsider the protocol that has been used thus far to find the mean bending modulus kc and Gaussian bending modulus k[overline]. With respect to previous predictions, the value of kc is reduced by a factor of two and the Gaussian bending modulus is less negative and much closer to zero. In line with experimental data we now find that k[overline] can also become positive. In this paper we use the non-ionic surfactants series of the type CnEm for illustration.

In this paper we discuss a new generalized time-dependent Ginzburg-Landau theory for the numerical calculation of polymer phase separation kinetics in 3D. The thermodynamic forces are obtained by a mean-field density functional method, using a Gaussian chain as a molecular model. The method is especially aimed at describing the formation kinetics of the irregular morphologies which are typical for many industrial systems. As proof of concept we present the formation of irregular morphologies in quenched symmetric and asymmetric block copolymer melts. (C) 1997 American Institute of Physics.

In quantum-mechanical/molecular-mechanical (QM/MM) treatment of chemical reactions in condensed phases, one solves the electronic Schrodinger equation for the solute (or an active site) under the electrostatic field from the environment. This Schrodinger equation depends parametrically on the solute nuclear coordinates R and the external electrostatic potential V. This fact suggests that one may use R and V as natural collective coordinates for describing the entire system, where V plays the role of collective solvent variables. In this paper such an (R,V) representation of the QM/MM canonical ensemble is described, with particular focus on how to treat charge transfer processes in this representation. As an example, the above method is applied to the proton-coupled electron transfer of a ubiquinol analog with phenoxyl radical in acetonitrile solvent. Ab initio free-energy surfaces are calculated as functions of R and V using the reference interaction site model self-consistent field method, the equilibrium points and the minimum free-energy crossing point are located in the (R,V) space, and then the kinetic isotope effects (KIEs) are evaluated approximately. The results suggest that a stiffer proton potential at the transition state may be responsible for unusual KIEs observed experimentally for related systems.

The fifth-order two-dimensional (2D) Raman signals have been calculated from the equilibrium and nonequilibrium (finite field) molecular dynamics simulations. The equilibrium method evaluates response functions with equilibrium trajectories, while the nonequilibrium method calculates a molecular polarizability from nonequilibrium trajectories for different pulse configurations and sequences. In this paper, we introduce an efficient algorithm which hybridizes the existing two methods to avoid the time-consuming calculations of the stability matrices which are inherent in the equilibrium method. Using nonequilibrium trajectories for a single laser excitation, we are able to dramatically simplify the sampling process. With this approach, the 2D Raman signals for liquid xenon, carbon disulfide, water, acetonitrile, and formamide are calculated and discussed. Intensities of 2D Raman signals are also estimated and the peak strength of formamide is found to be only five times smaller than that of carbon disulfide.

An examination of the finite system size effects on the calculated interfacial properties of the molten salt KI is described, as an extension of the work described in the preceding paper [J. Chem. Phys. 115, 8603 (2001)]. It is shown that, for system sizes beyond ∼1000 ions, the finite size effects are accounted for by the predictions of capillary wave (CW) theory, as in van der Waals liquids. Hence, there do not appear to be additional long-range effects arising from the Coulombic interactions. Techniques used to avoid truncation effects in the Coulombic and dispersion interactions appear to have eliminated system size dependent artefacts from these sources. The scaling behavior predicted from CW theory is used to predict the bulk surface tension for the chosen interaction potential, which is then compared with experimental values, and very good agreement found. Examination of the interfacial layers show that the local structure remains strongly charge ordered, but the surface is highly roughened by clus...

In this paper we introduce a three-dimensional version of the Mercedes-Benz model to describe water molecules. In this model van der Waals interactions and hydrogen bonds are given explicitly through a Lennard-Jones potential and a Gaussian orientation-dependent terms, respectively. At low temperature the model freezes forming Ice-I and it reproduces the main peaks of the experimental radial distribution function of water. In addition to these structural properties, the model also captures the thermodynamical anomalies of water: The anomalous density profile, the negative thermal expansivity, the large heat capacity, and the minimum in the isothermal compressibility.

The reactivity and spectra of formaldehyde isomers and dimeric complexes between them are studied with ab initio methods. A large number of complexes between H2CO, trans-HCOH, cis-HCOH is calculated. Infrared and Raman spectra of (H2CO)2 are calculated with relatively simple methods using spectroscopic masses and scaled force constants. In this way, the structure of dimers in matrices can be deduced. Hydroxycarbene (HCOH) plays a key role in a model that explains a large number of experimental facts of the nonzero pressure photochemistry. Hydroxycarbene forms complexes with H2CO; the stabilization is due to classical hydrogen bonds. HCOH is a new example of an ambiphilic carbene. Addition products are formed from HCOH···H2CO complexes. The calculations show that, in agreement with matrix experiments, glycoaldehyde and methanol are easily formed. The formation of trans-HCOH occurs through a dimeric interaction with the shifting hydrogen. This bimolecular process is 9.6 kcal/mol (6–31G*) in favor of the unimolecular conversion. cis-HCOH might be formed via a nonplanar transition state, where also stabilization at the carbenic center is possible. When higher concentrations of HCOH are available, a hydrogen exchange mechanism easily transfers hydroxycarbene back to H2CO. Several experiments are suggested in this paper; notably, molecular beam and isotopic-mixture experiments will give useful information. The involvement of HCOH in the light-induced formose reaction is suggested.