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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...

The quasi-Gaussian entropy (QGE) theory employs the fact that a free-energy change can be written as the moment-generating function of the appropriate probability distribution function of macroscopic fluctuations of an extensive property. By modeling this distribution, one obtains a model of free energy and resulting thermodynamics as a function of one state variable. In this paper the QGE theory has been extended towards theoretical models or equations of state (EOS’s) of the thermodynamics of semiclassical systems as a function of two state variables. Two “monovariate” QGE models are combined in the canonical ensemble: one based on fluctuations of the excess energy (the confined gamma state giving the temperature dependence) and the other based on fluctuations of the reduced electromagnetic moment [various models as derived in the preceding paper [Apol, Amadei, and Di Nola, J. Chem. Phys. 116, 4426 (2002)], giving the external field dependence]. This provides theoretical EOS’s for fluid systems as a function of both temperature and electromagnetic field. Special limits of these EOS’s are considered: the general weak-field EOS and the limit to a Curie’s law behavior. Based on experimental data of water and simulation data using the extended simple point charge (SPC/E) water model at 45.0 and 55.51 mol/dm3, the specific EOS based on a relatively simple combination of the confined gamma state model with a discrete uniform state field model accurately reproduces the dielectric properties of water at constant density, as the temperature dependence of the weak-field dielectric constant for gases and liquids, and the field dependence of the dielectric constant of liquids.

In a previous paper of this series [Paper III: Nakatsuji, J. Chem. Phys. 105, 2465 (2001)], the author showed a high potentiality of the extended coupled cluster (ECC) method to calculate the exact wave function of the ground state. In this paper, we propose ECC-configuration interaction (CI) method, which is an accurate useful method to calculate the excited states from the ECC wave function of the ground state. In contrast to the ECC method, the standard ECC-CI method is approximate, but we can make it exact by generalizing its excitation operator (ECC-CI general). The ECC-CI method is applicable not only to the excited states having the same spin-space symmetry as the ground state, but also to those having different spin-space symmetries and to the ionized and electron-attached states. The theoretical framework of the ECC-CI method is similar to that of the symmetry-adapted-cluster (SAC)-CI method proposed in 1978 by the present author. Next in this paper, we examine the performance of the methods proposed in this series of papers for a simple one-dimensional harmonic oscillator. The iterative configuration interaction (ICI) and ECC methods are examined for the ground state and the ICI-CI and ECC-CI methods for the excited states. The ICI method converges well to the exact ground state and the excited states are calculated nicely by the ICI-CI method in both the standard and general active spaces. In contrast to the simplest (S)ECC examined in Paper III, the ECC2 method shows quite a rapid convergence to the exact ground state, which enables us to calculate the true exact wave function in the ECC form. The ECC-CI methods in both the standard and general active spaces also work well to calculate the excited states. Thus, we conclude that the ICI and ECC approaches have a potentiality to provide useful method to calculate accurate wave functions of the ground and excited states. A merit of ECC is that it provides the exact wave function in a simple explicit form.

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.

The complexity of the absorption spectrum of NO2NO2 can be attributed to a conical intersection of the potential energy surfaces of the two lowest electronic states, the electronic ground state of 2A12A1 symmetry and the first electronically excited state of 2B22B2 symmetry. In a previous paper we reported on the feasibility of using the hyperfine splittings, specifically the Fermi-contact interaction, to determine the electronic ground state character of the excited vibronic states in the region just above the conical intersection; 10 000 to 14 000 cm−114 000 cm−1 above the electronic ground state. High-resolution spectra of a number of vibronic bands in this region were measured by exciting a supersonically cooled beam of NO2NO2 molecules with a narrow-band Ti:Sapphire ring laser. The energy absorbed by the molecules was detected by the use of a bolometer. In the region of interest, rovibronic interactions play no significant role, with the possible exception of the vibronic band at 12 658 cm−1,12 658 cm−1, so that the fine- and hyperfine structure of each rotational transition could be analyzed by using an effective Hamiltonian. In the previous paper we restricted ourselves to an analysis of transitions of the K⎯=0K−=0 stack. In the present paper we extend the analysis to transitions of the K⎯=1K−=1 stack, from which, in addition to hyperfine coupling constants, values of the AA rotational constants of the excited NO2NO2 molecules can be determined. Those rotational constants also contain information about the electronic composition of the vibronic states, and, moreover, about the geometry of the NO2NO2 molecule in the excited state of interest. The results of our analyses are compared with those obtained by other authors. The conclusion arrived at in our previous paper that determining Fermi-constants is useful to help characterize the vibronic bands, is corroborated. In addition, the AA rotational constants correspond to geometries that are consistent with the electronic composition of the relevant excited states as expected from the Fermi-constants., The complexity of the absorption spectrum of NO2 can be attributed to a conical intersection of the potential energy surfaces of the two lowest electronic states, the electronic ground state of 2A1 symmetry and the first electronically excited state of 2B2 symmetry. In a previous paper we reported on the feasibility of using the hyperfine splittings, specifically the Fermi-contact interaction, to determine the electronic ground state character of the excited vibronic states in the region just above the conical intersection; 10 000 to 14 000 cm−1 above the electronic ground state. High-resolution spectra of a number of vibronic bands in this region were measured by exciting a supersonically cooled beam of NO2 molecules with a narrow-band Ti:Sapphire ring laser. The energy absorbed by the molecules was detected by the use of a bolometer. In the region of interest, rovibronic interactions play no significant role, with the possible exception of the vibronic band at 12 658 cm−1, so that the fine- and hyperfine structure of each rotational transition could be analyzed by using an effective Hamiltonian. In the previous paper we restricted ourselves to an analysis of transitions of the K⎯=0 stack. In the present paper we extend the analysis to transitions of the K⎯=1 stack, from which, in addition to hyperfine coupling constants, values of the A rotational constants of the excited NO2 molecules can be determined. Those rotational constants also contain information about the electronic composition of the vibronic states, and, moreover, about the geometry of the NO2 molecule in the excited state of interest. The results of our analyses are compared with those obtained by other authors. The conclusion arrived at in our previous paper that determining Fermi-constants is useful to help characterize the vibronic bands, is corroborated. In addition, the A rotational constants correspond to geometries that are consistent with the electronic composition of the relevant excited states as expected from the Fermi-constants.

Nucleation rate data, obtained from expansion wave tube experiments, are reported for several vapor–gas mixtures at high pressure. Results are given for water–vapor in the presence of helium and nitrogen gas, and for n-nonane in helium and methane. For all these mixtures, carrier gas pressures of 10, 25, and 40 bar have been applied, with temperatures ranging from 230 to 250 K. An extended form of the nucleation theorem (in terms of the derivative of the nucleation rate with respect to carrier gas pressure) is derived, which appears to be very helpful in the interpretation of high pressure data. It can be used to obtain the carrier gas content of the critical nucleus directly from the pressure dependence of experimental nucleation rates. Combining this method with the theoretical considerations of part I of this paper [J. Chem. Phys. 111, 8524 (1999), preceding paper]: the nucleation behavior of water at high pressures of both helium and nitrogen can quantitatively be understood. For n-nonane in helium our "pressure perturbation approach" is also valid. For n-nonane in methane, however, this approach fails because of the high methane solubility in the liquid phase.

In 1954, Asakura and Oosawa1 explained that nonadsorbing macromolecules can induce attractive forces between colloidal particles. The effective pair interaction between the colloidal particles mediated by the non-adsorbing species is nowadays often termed the Asakura–Oosawa (AO) potential. This special issue of The Journal of Chemical Physics contains a collection of papers related to the concept introduced by Asakura and Oosawa. The late professor Oosawa contributed to this issue with a historical overview on the origin of the Asakura–Oosawa theory. Kurihara and Vincent discussed how, after a lag time of about 20 years, the theory was rediscovered in the 1970s via experimental studies on colloid–polymer mixtures. In the same period, Vrij independently found that excluded volume interactions in a colloidal dispersion containing an additional component have important consequences for the effective interactions, structure, and phase stability.

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.

We investigate the vibrational shift of beryllium oxide (BeO) in Xe matrix as well as in Ar matrix environments by mixed quantum-classical simulation and examine the origin of spectral shift in details. BeO is known to form strong chemical complex with single rare gas atom, and it is predicted from the gas phase calculations that vibrational frequencies are blueshifted by 78 cm^[-1] and 80 cm^[-1] upon formation of XeBeO and ArBeO, respectively. When the effects of other surrounding rare gas atoms are included by Monte Carlo simulations, it is found that the vibrational frequencies are redshifted by 21 cm^[-1] and 8 cm^[-1] from the isolated XeBeO and ArBeO complexes, respectively. The vibrational shift of XeBeO in Ar matrix is also calculated and compared with experimental data. In all simulations examined in this paper, the calculated vibrational frequency shifts from the isolated BeO molecule are in reasonable agreement with experimental values. The spectral shift due to the rare-gas-complex formation of RgBeO (Rg = Xe or Ar) is not negligible as seen in the previous studies, but it is shown in this paper that the effects of other surrounding rare gas atoms should be carefully taken into account for quantitative description of the spectral shifts and that these two effects are competing in vibrational spectroscopy of BeO in matrix environments.

With this Erratum, we provide corrections to certain mistakes appearing in the original publication.1 Namely, in Eq. (12), the -dependent Hamiltonian for the Hartree-Fock adiabatic connection lacks the external potential term. The correct equation is [Formula Presented]. The typos listed in the following all appear in the appendix. The parameter c in Eq. (A6) is wrong by a factor of two; the correct expression reads as follows: [Formula Presented]. In Eq. (A13), we have incorrectly used the parameter “c”; “c” has to be replaced by as defined in Eq. (A12). Also, the expression lacks the exchange energy. Thus, the proper expression reads as follows: [Formula Presented]. Finally, in Eqs. (A14) and (A15), the fractional powers appearing in the first terms are powers of the density and not of the position vector. Hence, [Formula Presented]. These corrections do not alter any of the results or conclusions shown in the paper.

The ultrafast electronic dynamics of pyrazine (C4N2H4) were studied by time-resolved photoelectron imaging (TRPEI) using the third (3ω, 4.7 eV) and fifth harmonics (5ω, 7.8 eV) of a femtosecond Ti:sapphire laser (ω). Although the photoionization signals due to the 5ω - 3ω and 3ω - 5ω pulse sequences overlapped near the time origin, we have successfully extracted their individual TRPEI signals using least squares fitting of the observed electron kinetic energy distributions. When the 5ω pulses preceded the 3ω pulses, the 5ω pulses predominantly excited the S4 (ππ∗, 1B1 u+1B2u) state. The photoionization signal from the S4 state generated by the time-delayed 3ω pulses was dominated by the D3(2B2g)←S4 photoionization process and exhibited a broad electron kinetic energy distribution, which rapidly downshifted in energy within 100 fs. Also observed were the photoionization signals for the 3s, 3pz, and 3py members of the Rydberg series converging to D0(2Ag). The Rydberg signals appeared immediately within our instrumental time resolution of 27 fs, indicating that these states are directly photoexcited from the ground state or populated from S4 within 27 fs. The 3s, 3pz, and 3py states exhibited single exponential decay with lifetimes of 94 ± 2, 89 ± 2, and 58 ± 1 fs, respectively. With the reverse pulse sequence of 3ω - 5ω, the ultrafast internal conversion (IC) from S2(ππ∗) to S1(nπ∗) was observed. The decay associated spectrum of S2 exhibited multiple bands ascribed to D0, D1, and D3, in agreement with the 3ω-pump and 6ω-probe experiment described in our preceding paper [T. Horio et al., J. Chem. Phys. 145, 044306 (2016)]. The electron kinetic energy and angular distributions from S1 populated by IC from S2 are also discussed.

In this paper, a previous coarse-grain model [J. T. Padding and W. J. Briels, J. Chem. Phys. 117, 925 (2002)]10.1063/1.1481859 to simulate melts of linear polymers has been adapted to simulate polymers with more complex hierarchies. Bond crossings between highly coarse-grained soft particles are prevented by applying an entanglement algorithm. We first test our method on a virtual branch point inside a linear chain to make sure it works effectively when linking two linear arms. Next, we apply our method to study the diffusive and rheological behaviors of a melt of three-armed stars. We find that the diffusive behavior of the three-armed star is very close to that of a linear polymer with the same molecular weight, while its rheological properties are close to those of a linear chain with molecular mass equal to that of the longest linear sub-chain in the star.

In this paper, a previous coarse-grain model [J. T. Padding and W. J. Briels, J. Chem. Phys. 117, 925 (2002)]10.1063/1.1481859 to simulate melts of linear polymers has been adapted to simulate polymers with more complex hierarchies. Bond crossings between highly coarse-grained soft particles are prevented by applying an entanglement algorithm. We first test our method on a virtual branch point inside a linear chain to make sure it works effectively when linking two linear arms. Next, we apply our method to study the diffusive and rheological behaviors of a melt of three-armed stars. We find that the diffusive behavior of the three-armed star is very close to that of a linear polymer with the same molecular weight, while its rheological properties are close to those of a linear chain with molecular mass equal to that of the longest linear sub-chain in the star.

Current efforts to characterize and study interstellar polycyclic aromatic hydrocarbons(PAHs) rely heavily on theoretically predicted infrared (IR) spectra. Generally, such studies use the scaled harmonic frequencies for band positions and double harmonic approximation for intensities of species, and then compare these calculated spectra with experimental spectra obtained under matrix isolation conditions. High-resolution gas-phase experimental spectroscopic studies have recently revealed that the double harmonic approximation is not sufficient for reliable spectra prediction. In this paper, we present the anharmonic theoretical spectra of three PAHs: naphthalene, anthracene, and tetracene, computed with a locally modified version of the SPECTRO program using Cartesian derivatives transformed from Gaussian 09 normal coordinate force constants. Proper treatments of Fermi resonances lead to an impressive improvement on the agreement between the observed and theoretical spectra, especially in the C–H stretching region. All major IR absorption features in the full-scale matrix-isolated spectra, the high-temperature gas-phase spectra, and the most recent high-resolution gas-phase spectra obtained under supersonically cooled molecular beam conditions in the CH-stretching region are assigned.

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.

Dissipative particle dynamics (DPD) is a mesoscopic simulation method for studying hydrodynamic behavior of complex fluids. Ideally, a mesoscopic model should correctly represent the thermodynamic and hydrodynamic properties of a real system beyond certain length and time scales. Traditionally defined DPD quite successfully mimics hydrodynamics but is not flexible enough to accurately describe the thermodynamics of a real system. The so-called multibody DPD (MDPD) is a pragmatic extension of the classical DPD that allows one to prescribe the thermodynamic behavior of a system with only a small performance impact. In an earlier paper [S. Y. Trofimov, E. L. F. Nies, and M. A. J. Michels, J. Chem. Phys. 117, 9383 (2002)] we much improved the accuracy of the MDPD model for strongly nonideal systems, which are of most practical interest. The ability to correctly reproduce the equation of state of realistic systems in turn makes simulations at constant pressure sensible and useful. This situation of constant-pressure conditions is very common in experimental studies of ??soft?? condensed matter but has so far remained unexplored with the traditional DPD. Here, as a proof of concept, we integrate a modified version of the Andersen barostat into our improved MDPD model and make an evaluation of the performance of the new model on a set of single- and multicomponent systems. The modification of the barostat suppresses the "unphysical" volume oscillations after a sudden pressure change and simplifies the equilibration of the system.

In the present study, variational path integral molecular dynamics and associated hybrid Monte Carlo (HMC) methods have been developed on the basis of a fourth order approximation of a density operator. To reveal various parameter dependence of physical quantities, we analytically solve one dimensional harmonic oscillators by the variational path integral; as a byproduct, we obtain the analytical expression of the discretized density matrix using the fourth order approximation for the oscillators. Then, we apply our methods to realistic systems like a water molecule and a para-hydrogen cluster. In the HMC, we adopt two level description to avoid the time consuming Hessian evaluation. For the systems examined in this paper, the HMC method is found to be about three times more efficient than the molecular dynamics method if appropriate HMC parameters are adopted; the advantage of the HMC method is suggested to be more evident for systems described by many body interaction. © 2016 Author(s)., after 12 months embargo

We report results from molecular dynamics simulations of the freezing transition of TIP5P water molecules confined between two parallel plates under the influence of a homogeneous external electric field, with magnitude of 5 V/nm, along the lateral direction. For water confined to a thickness of a trilayer we find two different phases of ice at a temperature of T=280 K. The transformation between the two, proton-ordered, ice phases is found to be a strong first-order transition. The low-density ice phase is built from hexagonal rings parallel to the confining walls and corresponds to the structure of cubic ice. The high-density ice phase has an in-plane rhombic symmetry of the oxygen atoms and larger distortion of hydrogen bond angles. The short-range order of the two ice phases is the same as the local structure of the two bilayer phases of liquid water found recently in the absence of an electric field [J. Chem. Phys. 119, 1694 (2003)]. These high- and low-density phases of water differ in local ordering at the level of the second shell of nearest neighbors. The results reported in this paper, show a close similarity between the local structure of the liquid phase and the short-range order of the corresponding solid phase. This similarity might be enhanced in water due to the deep attractive well characterizing hydrogen bond interactions. We also investigate the low-density ice phase confined to a thickness of 4, 5, and 8 molecular layers under the influence of an electric field at T=300 K. In general, we find that the degree of ordering decreases as the distance between the two confining walls increases. (C) 2004 American Institute of Physics.

In this paper we investigate the influence of self-affine roughness on the friction coefficient mu(f) of a rubber body under incomplete contact onto a solid surface. The roughness is characterized by the rms amplitude w, the correlation length xi, and the roughness exponent H. It is shown that with increasing surface roughening at short and/or long length scales (decreasing H and/or increasing ratio w/xi, respectively), the maximum of the friction coefficient mu(f) shifts to lower sliding velocities. The latter occurs only for conditions of incomplete contact for small contact length scales lambda (xi). In all cases, the friction coefficient mu(f) increases monotonically with decreasing roughness exponent H and/or increasing roughness ratio w/xi and attains its maximum value for sufficiently large contact length scales (xi).

This paper discusses a time-dependent density functional theory study of the effect of molecular structure on the excited state polarizability of conjugated molecules. A short phenylenevinylene oligomer containing three phenyl rings (PV2, distyryl benzene) is taken as a model system. Introduction of methyl substituents is shown to have only a small influence on the increase in polarizability upon excitation (the excess polarizability, Delta(alpha) over bar). Methoxy groups have a much larger effect but in this case Delta(alpha) over bar depends strongly on the dihedral angle between the side chain and the backbone of the molecule. If the central phenyl ring of PV2 has a meta-configuration rather than para, both the optical absorption spectrum and the excess polarizability change considerably. (C) 2003 American Institute of Physics.

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 this paper a combined experimental and quantum chemical study of the geometry and opto-electronic properties of unsubstituted and dialkoxy-sustituted phenylene–vinylene oligomers (PV’s) is presented. The optical absorption spectra for PV cations with different chain lengths and substitution patterns were measured using pulse radiolysis with time-resolved spectrophotometric detection from 1380 to 500 nm (0.9 to 2.5 eV). The geometries of the PV’s studied were optimized using density functional theory (DFT) for both the neutral and singly charged molecule. The spectra for the PV radical cations were then calculated using singly excited configuration interaction with an intermediate neglect of differential overlap reference wave function method together with the DFT geometry. The agreement between experimental and theoretical absorption energies is excellent; most of the calculated radical cation absorption energies are within 0.15 eV of the experimental values. The pattern of dialkoxy-substitution is found to have a large effect on the optical absorption spectrum of the cation. Using the calculated charge distribution it is shown that the degree of delocalization of the charge correlates with the energy of the lowest absorption band. If alkoxy side chains are present on some of the rings the positive charge tends to localize at those sites.

In this paper a combined experimental and quantum chemical study of the geometry and opto-electronic properties of unsubstituted and dialkoxy-sustituted phenylene–vinylene oligomers (PV’s) is presented. The optical absorption spectra for PV cations with different chain lengths and substitution patterns were measured using pulse radiolysis with time-resolved spectrophotometric detection from 1380 to 500 nm (0.9 to 2.5 eV). The geometries of the PV’s studied were optimized using density functional theory (DFT) for both the neutral and singly charged molecule. The spectra for the PV radical cations were then calculated using singly excited configuration interaction with an intermediate neglect of differential overlap reference wave function method together with the DFT geometry. The agreement between experimental and theoretical absorption energies is excellent; most of the calculated radical cation absorption energies are within 0.15 eV of the experimental values. The pattern of dialkoxy-substitution is found to have a large effect on the optical absorption spectrum of the cation. Using the calculated charge distribution it is shown that the degree of delocalization of the charge correlates with the energy of the lowest absorption band. If alkoxy side chains are present on some of the rings the positive charge tends to localize at those sites.

Nonlocal interactions play a prominent role in the optics of inhomogeneous systems. Classical discrete dipole descriptions take into account only electro-magnetic nonlocality. This is insufficient to describe correctly the inhomogeneous optical response (e.g., reflectance anisotropy) for covalently bonded systems like semiconductor surfaces. For those systems also a prominent quantum mechanical nonlocality exists. In a cellular description this can be understood easily from the behavior of the wave function. For strongly bonded systems the wave function extends across cell boundaries and when cells are polarized, neighboring cells get polarized as well. This quantum induction introduces nonlocal polarizabilities in the description. The technical details how discrete dipole models have to be adapted to use nonlocal polarizabilities in finite systems and crystalline slabs and surfaces are given in this paper. The modified method is called discrete cellular method.

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.

In this paper we show how relativistic effects can be included in the time-dependent density-functional theory (DFT) for the optical response properties of nonmetallic crystals. The dominant scalar relativistic effects have been included using the zeroth-order regular approximation (ZORA) in the ground-state DFT calculations, as well as in the time-dependent response calculations. We show that this theory can also be applied to indium antimonide in the zinc-blende structure, notwithstanding the fact that it turns into a semimetal when scalar relativistic effects are included. Results are given for the band structure, the static dielectric constant ε∞ and the dielectric function ε(ω), for the various levels on which relativity can be included, i.e., nonrelativistic, only in the ground-state, or also in the response calculation. Comparisons of our calculated results are made with experiment and other theoretical investigations. With the inclusion of scalar relativistic effects, the band structure of InSb becomes semimetallic within the local density approximation and we find a deviation of 5% from experiment for the static dielectric constant. Also the dielectric function is improved and the spectra are in good agreement with experiment, although the spectral features are shifted to somewhat lower energies compared to experiment.

In this paper we present the implementation of the two-component scaled zeroth-order regular approximation (ZORA) method in the molecular electronic structure package GAMESS-UK. It is the first application of this method, which was earlier investigated in the context of density functional theory, in molecular ab initio basis set calculations. The performance of the method is tested in atomic calculations, which we can compare with numerical results, on xenon and radon and in molecular calculations on the molecules AgH, HI, I2, AuH, TlH, and Bi2. In calculations on the I2 molecule we investigated the effect of the different approaches regarding the internal Coulomb matrix used in the ZORA method. For the remaining molecules we computed harmonic frequencies and bond lengths. It is shown that the scaled ZORA approach is a cost-effective alternative to the Dirac–Fock method.

The key characteristics of electronic excitations of many-electron systems, the excitation energies ωα and the oscillator strengths fα, can be obtained from linear response theory. In one-electron models and within the adiabatic approximation, the zeros of the inverse response matrix, which occur at the excitation energies, can be obtained from a simple diagonalization. Particular cases are the eigenvalue equations of time-dependent density functional theory (TDDFT), time-dependent density matrix functional theory, and the recently developed phase-including natural orbital (PINO) functional theory. In this paper, an expression for the oscillator strengths fα of the electronic excitations is derived within adiabatic response PINO theory. The fα are expressed through the eigenvectors of the PINO inverse response matrix and the dipole integrals. They are calculated with the phaseincluding natural orbital functional for two-electron systems adapted from the work of Lowdin ¨ and Shull on two-electron systems (the phase-including Löwdin-Shull functional). The PINO calculations reproduce the reference fα values for all considered excitations and bond distances R of the prototype molecules H2 and HeH+ very well (perfectly, if the correct choice of the phases in the functional is made). Remarkably, the quality is still very good when the response matrices are severely restricted to almost TDDFT size, i.e., involving in addition to the occupied-virtual orbital pairs just (HOMO+1)-virtual pairs (R1) and possibly (HOMO+2)-virtual pairs (R2). The shape of the curves fα(R) is rationalized with a decomposition analysis of the transition dipole moments. peerReviewed

In this paper a detailed theoretical analysis is presented of the temperature dependent radiative decay in aggregates of pseudoisocyanine (PIC). Our approach extends the original linear exciton-phonon coupling model including static disorder and second order exciton-phonon interactions. It is shown that for a one-dimensional exciton model neither of these additional effects alone or in combination with linear electron–phonon coupling can explain the steep rise in radiative lifetime at 40 K observed in the J-aggregate of PIC. However, when the aggregate assembles into a two-dimensional bricklike structure its radiative dynamics can be simulated, with linear exciton-optical phonon coupling as the only source for exciton scattering. Exciton-phonon scattering transfers oscillator strength from the k=0 state to other band states and also generates a nonequilibrium population among the exciton states, which persists during the superradiant decay. These effects together explain the marked temperature dependence of the radiative lifetime of the PIC J aggregate. When disorder limits the coherence length at low temperatures to a few molecules, as seems the case in several light harvesting complexes, the exciton population can equilibrate on the time scale of the superradiance. This situation pertains to the strong collision limit of the master equation, where the radiative decay is insensitive to details of the electron–phonon coupling, but only senses change in the thermal population among the exciton states.

The visible absorption spectrum of NO2 is very dense and irregular, and shows signs of a chaotic frequency and intensity distribution in the higher energy region. The complexity of the spectrum is related to a conical intersection of the potential energy surfaces of the two lowest electronic states. Above the conical intersection strong vibronic interactions lead to hybrid eigenstates, which can be viewed as mixtures of low vibrational levels of the electronically excited state and high vibrational levels of the electronic ground state. As a contribution to the elucidation of the nature of the vibronic bands of NO2 we have measured high-resolution spectra of a number of vibronic bands in the region between 10 000 and 14 000 cm−1 by exciting a supersonically cooled beam of NO2 molecules with a narrow-band Ti:Sapphire ring laser. The energy absorbed by the molecules was detected by a bolometer, and in some cases, laser-induced fluorescence was detected. The hyperfine structure is dominated by the Fermi-contact interaction and the magnitude of this interaction is a direct measure of the (electronic) composition of the hybrid eigenstates. In the present paper we have restricted our analysis to transitions of K⎯=0 stacks. The fine- and hyperfine structure of each rotational transition can be analyzed by using an effective Hamiltonian approach. The very good agreement that is found between the calculated transition strengths and the measured line intensities is evidence that in the spectral region studied, rovibronic interactions play a minor role. The composition of the hybrid eigenstates is compared with ab initio calculations reported in the literature, leading to the conclusion that measurements of the hyperfine structure are a helpful tool in characterizing vibronic bands.

The visible absorption spectrum of NO2 is very dense and irregular, and shows signs of a chaotic frequency and intensity distribution in the higher energy region. The complexity of the spectrum is related to a conical intersection of the potential energy surfaces of the two lowest electronic states. Above the conical intersection strong vibronic interactions lead to hybrid eigenstates, which can be viewed as mixtures of low vibrational levels of the electronically excited state and high vibrational levels of the electronic ground state. As a contribution to the elucidation of the nature of the vibronic bands of NO2 we have measured high-resolution spectra of a number of vibronic bands in the region between 10 000 and 14 000 cm−1 by exciting a supersonically cooled beam of NO2 molecules with a narrow-band Ti:Sapphire ring laser. The energy absorbed by the molecules was detected by a bolometer, and in some cases, laser-induced fluorescence was detected. The hyperfine structure is dominated by the Fermi-contact interaction and the magnitude of this interaction is a direct measure of the (electronic) composition of the hybrid eigenstates. In the present paper we have restricted our analysis to transitions of K⎯=0 stacks. The fine- and hyperfine structure of each rotational transition can be analyzed by using an effective Hamiltonian approach. The very good agreement that is found between the calculated transition strengths and the measured line intensities is evidence that in the spectral region studied, rovibronic interactions play a minor role. The composition of the hybrid eigenstates is compared with ab initio calculations reported in the literature, leading to the conclusion that measurements of the hyperfine structure are a helpful tool in characterizing vibronic bands.

In this paper we present time-dependent density functional calculations on frequency-dependent first (β) and second (γ) hyperpolarizabilities for the set of small molecules, N2, CO2, CS2, C2H4, NH3, CO, HF, H2O, and CH4, and compare them to Hartree–Fock and correlated ab initio calculations, as well as to experimental results. Both the static hyperpolarizabilities and the frequency dispersion are studied. Three approximations to the exchange-correlation (xc) potential are used: the widely used Local Density Approximation (LDA), the Becke–Lee–Yang–Parr (BLYP) Generalized Gradient Approximation (GGA), as well as the asymptotically correct Van Leeuwen–Baerends (LB94) potential. For the functional derivatives of the xc potential the Adiabatic Local Density Approximation (ALDA) is used. We have attempted to estimate the intrinsic quality of these methods by using large basis sets, augmented with several diffuse functions, yielding good agreement with recent numerical static LDA results. Contrary to claims which have appeared in the literature on the basis of smaller studies involving basis sets of lesser quality, we find that the static LDA results for β and γ are severely overestimated, and do not improve upon the (underestimated) Hartree–Fock results. No improvement is provided by the BLYP potential which suffers from the same incorrect asymptotic behavior as the LDA potential. The results are however clearly improved upon by the LB94 potential, which leads to underestimated results, slightly improving the Hartree–Fock results. The LDA and BLYP potentials overestimate the frequency dependence as well, which is once again improved by the LB94 potential. Future improvements are expected to come from improved models for asymptotically correct exchange-correlation potentials. Apart from the LB94 potential used in this work, several other asymptotically correct potentials have recently been suggested in the literature and can also be expected to improve considerably upon the relatively poor LDA and GGA results, for both the static properties and their frequency dependence.

In the present paper we consider nonlinear elasticity and friction of grafted persistent chains, which are highly stretched in the normal to the surface direction due to orientational interactions. We examine the normal and the lateral forces both in equilibrium and under shear sliding when the monolayer is confined by a bare surface. We show that in the confined monolayer in equilibrium the tilted orientation of the director becomes stable. In the sliding regime the friction force passes through a maximum value. The additional normal force in the sliding regime, when the distance between the surfaces is fixed, is also considered. We show that this force is attractive for small velocities and becomes repulsive for high velocities after the friction force passes through the maximum value.

In this paper, we study the evolution of phase-separating binary mixtures which are subjected to alternate cooling and heating cycles. An initially homogeneous mixture is rapidly quenched to a temperature T(1)T(c), where T(c) is the critical temperature. The mixture undergoes phase separation for a while and is then suddenly heated to a temperature T(2)T(c). These cycles are repeated to create a domain morphology with multiple length scales, i.e., the structure factor is characterized by multiple peaks. For phase separation in d = 2 systems, we present numerical and analytical results for the emergence and growth of this multiple-scale morphology.

In this paper we apply nonlocal kinetic coupling to the dynamic mean-field density functional method, which is derived from generalized time-dependent Ginzburg-Landau theory. The method is applied to the mesoscopic dynamics of copolymer melts, which was previously simulated using a local coupling approximation. We discuss the general theory of time evolution of density variables with general kinetic coefficients developed by Kawasaki and Sekimoto, and especially the limits of the theory that yield the local coupling approximation, the collective Rouse dynamics model, and the reptation dynamics model. We show bow a simple approximation to the Rouse dynamics model leads to a feasible numerical model that includes the essential physical features of nonlocal kinetic coupling. This results in a dynamic equation for the external potential instead of the density which allows us to perform calculations of microphase separation in copolymer melts with increased relevance to experimental results. As may be expected from a numerical model that includes nonlocal kinetic coupling, the numerical results show an increased computational efficiency, less defects in the final morphology, and a faster increase of the order parameter compared to local kinetic coupling. (C) 1997 American Institute of Physics.

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.

The flux-flux correlation function formalism is a standard and widely used approach for the computation of reaction rates. In this paper we introduce a method to compute the classical and quantum flux-flux correlation functions for anharmonic barriers essentially analytically through the use of the classical and quantum normal forms. In the quantum case we show that the quantum normal form reduces the computation of the flux-flux correlation function to that of an effective one dimensional anharmonic barrier. The example of the computation of the quantum flux-flux correlation function for a fourth order anharmonic barrier is worked out in detail, and we present an analytical expression for the quantum mechanical microcanonical flux-flux correlation function. We then give a discussion of the short-time and harmonic limits., 9 pages, 2 figures

Low-frequency intermolecular dynamics in liquids is studied by ultrafast four- and six-wave mixing. The theory of these nonlinear optical processes is given for electronically nonresonant optical interactions up to fifth order in the electric field. The Born-Oppenheimer approximation is used to separate the motional part of the response functions from coordinate independent electronic hyperpolarizabilities. A large variety of experiments, involving far-infrared absorption, ordinary Rayleigh-Raman or hyper Rayleigh-Raman scattering is covered by this theory. The response in nonresonant six-wave mixing comprises four dynamically different processes. It is shown that one of the terms contains information on the time scale(s) of intermolecular dynamics, that is not available from lower-order nonresonant experiments. For instance, homogenous and inhomogeneous contributions to line broadening can be distinguished. The optical response of harmonic nuclear motion is calculated for nonlinear coordinate dependence of the polarizabilities. Results for level-dependent and level-independent damping of the motion are compared. It is shown that level-dependent damping destroys the interference between different quantum mechanical pathways, yielding an extra contribution to the fifth-order response that has not been discussed before. When two or more nuclear modes determine the optical response, their relative contributions to the four- and six-wave mixing signals are in general different. These contributions are determined by the coordinate dependence of the electronic polarizability, which is usually not fully known, Model calculations are presented for the dynamic parameters of liquid CS2. The theory of this paper will be employed in Part II, to analyze experimental results on femtosecond four- and six-wave mixing.

The exchange-correlation potentials v xc which are currently fashionable in density functional theory ~DFT!, such as those obtained from the local density approximation ~LDA! or generalized gradient approximations ~GGAs!, all suffer from incorrect asymptotic behavior. In atomic calculations, this leads to substantial overestimations of both the static polarizability and the frequency dependence of this property. In the present paper, it is shown that the errors in atomic static dipole and quadrupole polarizabilities are reduced by almost an order of magnitude, if a recently proposed model potential with correct Coulombic long-range behavior is used. The frequency dependence is improved similarly. The model potential also removes the overestimation in molecular polarizabilities, leading to slight improvements for average molecular polarizabilities and their frequency dependence. For the polarizability anisotropy we find that the model potential results do not improve over the LDA and GGA results. Our method for calculating frequency-dependent molecular response properties within time-dependent DFT, which we described in more detail elsewhere, is summarized. © 1996 American Institute of Physics.@S0021-9606~96!02031-4#

In this paper, an extensive analysis of free volume related properties of a lipid membrane is given. Using percolation theory, and comparing the free volume properties to those of a soft polymer, additional insights are obtained. The analyses are discussed within the framework of the four region model. It is concluded that the four regions have very different free volume properties. The region containing the dense part of the lipid tails resembles a soft polymer membrane to a large extent. The middle part of the membrane is more similar to a low density alkane. The consequences of the computed free volume properties on the permeation process of small penetrants are discussed. (C) 1996 American Institute of physics.

A new theory is presented for calculating the Helmholtz free energy based on the potential energy distribution function. The usual expressions of free energy, internal energy and entropy involving the partition function are rephrased in terms of the potential energy distribution function, which must be a near Gaussian one, according to the central limit theorem. We obtained expressions for the free energy and entropy with respect to the ideal gas, in terms of the potential energy moments. These can be linked to the average potential energy and its derivatives in temperature. Using thermodynamical relationships we also produce a general differential equation for the free energy as a function of temperature at fixed volume. In this paper we investigate possible exact and approximated solutions. The method was tested on a theoretical model for a solid (classical harmonic solid) and some experimental liquids. The harmonic solid has an energy distribution, which can be derived exactly from the theory. Experimental free energies of water and methanol could be reproduced very well over a temperature range of more than 300 K. For water, where the appropriate experimental data were available, also the energy and heat capacity could be reproduced very well. (C) 1996 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.

In this paper, we describe a numerical method for the calculation of collective diffusion relaxation mechanisms in quenched block copolymer melts. The method entails the repeated calculation of two opposing fields-an external potential field U, conjugate to the density field rho, and an energetic interaction field E. The external field is calculated by numerical inversion of the density functionals and the energetic interaction field is calculated directly by integration over the density field. When the two fields are balanced U = E, we recover the self-consistent field solutions; when the two fields are off balance, the spatial gradient of E-U is the thermodynamic force which drives the collective diffusion. We introduce a simple local coupling approximation for the Onsager kinetic coefficients of short freely jointed chains in weakly ordered systems. Fluctuations are added by incorporation of a random Langevin force in the diffusion equation. Numerical results of decomposition in symmetric and asymmetric diblock copolymer melts indicate that the method is capable of describing extremely slow defect annihilation relaxation modes. We find that in the nonlinear regime, the density patterns evolve to metastable states, in which isolated defects separate relatively well-ordered crystalline microdomains. These final states are typical for many industrial applications of incompletely relaxed copolymer melts.