Nonadiabatic molecular dynamics simulations of correlated electrons in solution. 1. Full configuration interaction (CI) excited-state relaxation dynamics of hydrated dielectrons

The hydrated dielectron is composed of two excess electrons dissolved in liquid water that occupy a single cavity; in both its singlet and triplet spin states there is a significant exchange interaction so the two electrons cannot be considered to be independent. In this paper and the following paper,we present the results of mixed quantum/classical molecular dynamics simulations of the nonadiabatic relaxation dynamics of photoexcited hydrated dielectrons, where we use full configuration interaction (CI) to solve for the two-electron wave function at every simulation time step. To the best of our knowledge, this represents the first systematic treatment of excited-state solvation dynamics where the multiple-electron problem is solved exactly. The simulations show that the effects of exchange and correlation contribute significantly to the relaxation dynamics. For example, spin-singlet dielectrons relax to the ground state on a time scale similar to that of single electrons excited at the same energy, but spin-triplet dielectrons relax much faster. The difference in relaxation dynamics is caused by exchange and correlation: The Pauli exclusion principle imposes very different electronic structure when the electrons' spins are singlet paired than when they are triplet paired, altering the available nonadiabatic relaxation pathways. In addition, we monitor how electronic correlation changes dynamically during nonadiabatic relaxation and show that solvent dynamics cause electron correlation to evolve quite differently for singlet and triplet dielectrons. Despite such differences, our calculations show that both spin states are stable to excited-state dissociation, but that the excited-state stability has different origins for the two spin states. For singlet dielectrons, the stability depends on whether the solvent structure can rearrange to create a second cavity before the ground state is reached. For triplet dielectrons, in contrast, electronic correlation ensures that the two electrons do not dissociate, even if the dielectron is artificially kept from reaching the ground state. In addition, both singlet and triplet dielectrons change shape dramatically during relaxation, so that linear response fails to describe the solvation dynamics for either spin state. In the following paper (Larsen, R. E.; Schwartz, B. J. J. Phys. Chem. B 2006, 110, 9692), we use these simulations to calculate the pump-probe spectroscopic signal expected for photoexcited hydrated dielectrons and to predict an experiment to observe hydrated dielectrons directly.     

Ab initio study of the thermodynamic and kinetic stability of the ammonium radical

An increasing interest in the possible existence of the NH₄ radical has emerged in recent years. In this paper we report an ab initio UHF CI study of the ammonium radical, an investigation of parts of the energy surface around NH₄ and a theoretical prediction of the kinetic parameters of the radical formation and dissociation reactions within the framework of the TST theory. The ground state of the ammonium radical appears to be of the Rydberg type. Its ionization potential is found to be 4.29 eV. The NH₄ formation reaction from NH₂ + H₂ is very slightly exothermic whereas the reaction from NH₃ + H is slightly endothermic. We find a transition state of C_3v symmetry for the dissociation of NH₄ into NH₃ + H. The insertion of H₂ into NH₂ occurs according to a two-step mechanism whose determining step corresponds to the crossing of a saddle point with C_s symmetry previously obtained in the study of the reaction NH₂ + H₂ → NH₃ + H. Finally, we predict for NH₄ and ND₄ lifetimes of 0.1 and 1.4 μs respectively.     

Full configuration interaction for the benzyl radical

The electronic structure of the benzyl radical in its ground state has been computed using a model Hamiltonian due to Pariser–Parr with full configuration interaction as well as with different truncated configurational sets built on SCF open-shell orbitals. The correlation energy corresponding to this model was found to be equal to –0.929722 eV. With the singly excited configurations only 18% of this energy is taken into account. By extending the basis to include the doubly excited configurations one can account for 94% of the correlation energy. An analysis of the accuracy of the proton hyperfine splitting calculation caused by inaccurate computation of the wave function is given. If only singly and even doubly excited configurations are taken into account one cannot hope to obtain splittings with an accuracy of more than 0.5 g. Inclusion of triply excited configurations lowers this error by one order. In addition, the use of the simple McConnell relation may lead to an error in splitting calculations of no less than 1.5 g.     

On the thermodynamic and kinetic stability of nonequilibrium systems

A criterion of evolution of nonequilibrium systems in the region of stable states was formulated.     

Full configuration interaction calculation of Be3

The full configuration interaction (FCI) study of the ground state of the neutral beryllium trimer has been performed using an atomic natural orbitals [3s2p1d] basis set. Both triangular and linear structures have been considered for the Be(3) cluster. The optimal geometry for the equilateral triangle has been calculated. The potential energy cut sections along the normal a(1)(') mode and one of the components of the e(') mode have then been studied. The FCI symmetric atomization potential of the linear cluster is also reported. It shows a secondary van der Waals minimum at a long bond distance. All singular points in the potential energy curves are characterized. Other properties, like dissociation energies D(e) and vibrational frequencies, have been estimated from a fourth-order fitting of a large range of points around the minima. The calculated FCI wave number values for the nu(1) and nu(2) normal modes are (467.33+/-0.43) cm(-1) and (390.77+/-0.56) cm(-1).     

Full configuration interaction study of the ground state of closed-shell cyclic PPP polyenes

Full configuration interaction (FCI ) calculations are reported for the closed-shell cyclic polyenes C_NH_N (N = 6, 10, 14, 18) in the Pariser–Parr–Pople (PPP ) approximation, as a function of the hopping parameter β. A wide range of values of β is considered, from a highly correlated situation, β = 0, to a very weakly correlated limit, β = ?10 eV. An estimate of the role of higher than two-body connected cluster components was done, through a partial (i.e., limited to two-body terms in the exponent) cluster analysis performed on the FCI wave function. The comparison with the approximate coupled pair theory that accounts for quadruply excited clusters [see P. Piecuch and J. Paldus, Theor. Chim. Acta 78 , 65 (1990)] shows a good agreement in the whole range of the hopping parameter, particularly when the contribution of connected triples excitations is also taken into account. © 1994 John Wiley & Sons, Inc.     

Origin of short-range repulsion between hydrated phospholipid bilayers: a computer simulation study

The grand canonical Monte Carlo technique is used to simulate the pressure-distance dependence for supported dilauroylphosphatidylethanolamine (DLPE) membranes. The intra- and intermolecular interactions in the system are described with a combination of an AMBER-based force field for DLPE and a TIP4P model for water. To improve the balance between the pair interactions of like and unlike molecules, the water-lipid interaction potentials are scaled to reproduce the hydration level and intermembrane separation at full hydration. It is found that the short-range water-mediated repulsion originates from the hydration component of the intermembrane pressure, whereas the direct interaction between the membranes remains attractive throughout the pressure range studied (0-5 kbar).     

Thermoanalytical approach to the study of the kinetic and thermodynamic stability of coordination compounds and clathrates

The possibilities of the modern thermoanalytical methods for the study of the kinetic lability and thermodynamic stability of coordination compounds and inclusion compounds are discussed. The nonisothermal kinetics allowed to obtain the kinetic stability series of compounds (iso-entropy, iso-enthalpy and with iso-kinetic temperature), these series are considered from the point of view of the ligands substitution mechanism. The quasi-equilibrium thermogravimetry was used for the forming of thermodynamic stability series and for the search of the iso-equilibrium temperature.

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Zusammenfassung Es werden die Möglichkeiten moderner thermoanalytischer Methoden für die Untersuchung der kinetischen Labilität und der thermodynamischen Stabilität von Koordinations- und Einschlußverbindungen diskutiert. Die nichtisotherme Kinetik erlaubt die Erstellung von kinetischen Stabilitätsreihenfolgen der Verbindungen (Iso-Entropie, Iso-Enthalpie und mit isokinetischer Temperatur). Diese Reihenfolgen wurden auch vom Gesichtspunkt des Mechanismus der Ligandensubstitution her bewertet. Eine quasi-Gleichgewichts-Thermogravimetrie wurde zur Erstellung der Reihenfolge der thermodynamischen Stabilität und zur Ermittlung der iso-Gleichgewichtstemperatur benutzt.

     

Full configuration interaction calculation of BeH adiabatic states

An all-electron full configuration interaction (FCI) calculation of the adiabatic potential energy curves of some of the lower states of BeH molecule is presented. A moderately large ANO basis set of atomic natural orbitals (ANO) augmented with Rydberg functions has been used in order to describe the valence and Rydberg states and their interactions. The Rydberg set of ANOs has been placed on the Be at all bond distances. So, the basis set can be described as 4s3p2d1f3s2p1d(BeH)+4s4p2d(Be). The dipole moments of several states and transition dipole strengths from the ground state are also reported as a function of the R(Be-H) distance. The position and the number of states involved in several avoided crossings present in this system have been discussed. Spectroscopic parameters have been calculated from a number of the vibrational states that result from the adiabatic curves except for some states in which this would be completely nonsense, as it is the case for the very distorted curves of the 3s and 3p (2)Sigma(+) states or the double-well potential of the 4p (2)Pi state. The so-called "D complex" at 54 050 cm(-1) (185.0 nm) is resolved into the three 3d substates ((2)Sigma(+),(2)Pi,(2)Delta). A diexcited valence state is calculated as the lowest state of (2)Sigma(-) symmetry and its spectroscopic parameters are reported, as well as those of the 2 (2)Delta (4d) state The adiabatic curve of the 4 (2)Sigma(+) state shows a swallow well at large distances (around 4.1 A) as a result of an avoided crossing with the 3 (2)Sigma(+) state. The probability that some vibrational levels of this well could be populated is discussed within an approached Landau-Zerner model and is found to be high. No evidence is found of the E(4ssigma) (2)Sigma(+) state in the region of the "D complex". Instead, the spectroscopic properties obtained from the (4ssigma) 6 (2)Sigma(+) adiabatic curve of the present work seem to agree with those of the experimental F(4psigma) (2)Sigma(+) state. The FCI calculations provide benchmark results for other correlation models for the open-shell BeH system and evidence both the limitations and capabilities of the basis set.     

Nonadditivity and the stability of Ag3. A multireference configuration interaction study

Variational (?30 000 determinants) and perturbational (?3.5 million determinants) Localized Multireference Configuration Interaction (LMRCI) calculations includingf polarization functions are made to study the role played by the three-body terms in the stabilization energy of three selected geometries of the silver trimer: linear, equilateral and a Jahn-Teller obtuse triangle conformation. A comparative analysis of the relative stability of these geometries is done through a many-body decomposition of the interaction energy. Like in Cu₃, the most symmetrical arrangement (i.e. an equilateral triangle) is found to be less stable than the obtuse triangle because it has the highest three-body repulsion energy. The absolute minimum is the obtuse triangle having a Jahn-Teller stabilization energy of 328 cm^?1. Unlike Cu₃, the linear geometry is found to be less stable than the equilateral by 1282cm^?1. Results show again the importance of three-body terms in the total interaction energy of these trimers.     

Full configuration interaction approach to the few-electron problem in artificial atoms

We present a new high performance configuration interaction code optimally designed for the calculation of the lowest-energy eigenstates of a few electrons in semiconductor quantum dots (also called artificial atoms) in the strong interaction regime. The implementation relies on a single-particle representation, but it is independent of the choice of the single-particle basis and, therefore, of the details of the device and configuration of external fields. Assuming no truncation of the Fock space of Slater determinants generated from the chosen single-particle basis, the code may tackle regimes where Coulomb interaction very effectively mixes many determinants. Typical strongly correlated systems lead to very large diagonalization problems; in our implementation, the secular equation is reduced to its minimal rank by exploiting the symmetry of the effective-mass interacting Hamiltonian, including square total spin. The resulting Hamiltonian is diagonalized via parallel implementation of the Lanczos algorithm. The code gives access to both wave functions and energies of first excited states. Excellent code scalability in a parallel environment is demonstrated; accuracy is tested for the case of up to eight electrons confined in a two-dimensional harmonic trap as the density is progressively diluted up to the Wigner regime, where correlations become dominant. Comparison with previous quantum Monte Carlo simulations in the Wigner regime demonstrates power and flexibility of the method.     

Full spin-orbit configuration interaction calculations on electronic states of LiBe

Ab initio calculations are reported for the simplest heteronuclear metal cluster, LiBe. Full spin-orbit configuration interaction calculations in the context of relativistic effective core potentials lead to accurate potential energy curves for low-lying states. Results are compared with recent experimental observations and with all electron multi-reference configuration interaction calculations.     

Full configuration interaction calculation of the low lying valence and Rydberg states of BeH

The all-electron full configuration interaction (FCI) vertical excitation energies for some low lying valence and Rydberg excited states of BeH are presented in this article. A basis set of valence atomic natural orbitals has been augmented with a series of Rydberg orbitals that have been generated as centered onto the Be atom. The resulting basis set can be described as 4s2p1d/2s1p (Be/H) + 4s4p3d. It allows to calculate Rydberg states up to n= {3,4,5} of the s, p, and d series of Rydberg states. The FCI vertical ionization potential for the same basis set and geometry amounts to 8.298 eV. Other properties such as FCI electric dipole and quadrupole moments and FCI transition dipole and quadrupole moments have also been calculated. The results provide a set of benchmark values for energies, wave functions, properties, and transition properties for the five electron BeH molecule. Most of the states have large multiconfigurational character in spite of their essentially single excited nature and a number of them present an important Rydberg-valence mixing that is achieved through the mixed nature of the particle MO of the single excitations.     

Full configuration interaction calculation of singlet excited states of Be3

The full configuration interaction (FCI) study of the singlets vertical spectrum of the neutral beryllium trimer has been performed using atomic natural orbitals [3s2p1d] basis set. The FCI triangular equilibrium structure of the ground state has been used to calculate the FCI vertical excitation energies up to 4.8 eV. The FCI vertical ionization potential for the same geometry and basis set amounts to 7.6292 eV. The FCI dipole and quadrupole transition moments from the ground state are reported as well. The FCI electric quadrupole moment of the X (3)A(1) (') ground state has been also calculated with the same basis set (Theta(zz)=-2.6461 a.u., Theta(xx)=Theta(yy)=-1/2Theta(zz)). Twelve of the 19 calculated excited singlets are doubly excited states. Most of the states have large multiconfigurational character. These results provide benchmark values for electronic correlation multireference methods. (4ex6MO)CAS-SDCI values for the same energies and properties are also reported.     

Multireference configuration interaction study of bromocarbenes

Multireference configuration interaction (MRCI) calculations of the lowest singlet X(1A') and triplet ?((3)A') states as well as the first excited singlet ?((1)A') state have been performed for a series of bromocarbenes: CHBr, CFBr, CClBr, CBr(2), and CIBr. The MRCI calculations were performed with correlation consistent basis sets of valence triple-ζ plus polarization quality, employing a full-valence active space of 18 electrons in 12 orbitals (12 and 9, respectively, for CHBr). Results obtained include equilibrium geometries and harmonic vibrational frequencies for each of the electronic states, along with ?((3)A') ← X((1)A') singlet-triplet gaps and ?((1)A') ← X((1)A') transition energies. Comparisons have been made with previous computational and experimental results where available. The MRCI calculations presented in this work provide a comprehensive series of results at a consistent high level of theory for all of the bromocarbenes.     

A thermodynamic and kinetic study on the stability of the conformational states of N-acetyl-proline-methylamide by IR. Spectroscopy and chemical relaxation

N-Acetyl-proline-methylamide (APMA) was synthesized by the mixed anhydride method and investigated by IR. spectroscopy and chemical relaxation measurements. The temperature-induced variation of the IR. absorption bands of the internally hydrogen bonded (b) and of the extended, unbonded (e) species at 3330 and 3450 cm^?1 respectively, were used to evaluate the molar absorptivities, a(b) = 280 and a(e) = 50 l/mol · cm, the equilibrium constant K = 0.70, and the molar enthalpy of reaction ΔH = ? 2280 ± 60 cal/mol. The entropy was estimated to be in the range ? 8 to ? 9 e.u. The reaction rates of this conformational transition were measured by the chemical dipole field effect. The relaxation time of the rate process is τ = 2.7 · 10^?9s, the rate constant for the formation of the hydrogen bond k(b) is 2.2 · 10⁸ s^?1, and that for the unfolding accompanied by the breakage of the amide hydrogen bond k(e) is 1.5 · 10⁸s^?1.     

The interaction of dolomite surfaces with metal impurities: a computer simulation study

This study investigates the behaviour of selected, morphologically important surfaces of dolomite (CaMg(CO3)2), using computational modelling techniques. Interatomic potential methods have been used to examine impurity substitution at cationic sites in these surfaces. Environmentally prevalent cations were studied to this end, namely Ni2+, Co2+, Zn2+, Fe2+, Mn2+ and Cd2+, all of which are also found as end-member carbonate minerals. Solid-solution substitution was investigated and showed that Cd and Mn will substitute from their end-member carbonate phase at either dolomite cation site. Mn is found to preferentially substitute at Mg sites, in agreement with experimental findings. For Ni2+, Co2+ and Zn2+, the magnitude of substitution energies is approximately equal for all surfaces, with the exception of the (1014) surface. However, for the larger cations, a far greater disparity in substitution energies is observed. At a stepped surface, analogous substitutions were performed and it was found that substitution energies for all impurity cations were reduced, indicating that uptake is more viable during growth. The predominant surface, the (1014), was solvated with a monolayer of water in order to investigate the influence of hydration on substitution energetics. The addition of water changes the relative preference for substitution of the different cations. Under aqueous conditions, the substitution energy is determined by three competing factors, the relative importance of which cannot be predicted without this type of computational investigation.     

A Monte Carlo computer simulation of the thermodynamic properties of solid N2

Selected thermodynamic properties of solid N₂ are investigated by carrying out classical Monte Carlo calculations for a system of 108 rigid linear molecules initially disposed in the cubic Pa3 structure and interacting via Mie—Lennard-Jones pair potentials between their ends. One run was carried out at (T = 96.4 K, V = 23.6 cm³ mole^?I) using a (12-6) potential, the other at T = 192.8 K and the same volume using a (9-6) potential. Only the latter potential appears to correlate well with recent experimental pVT data. In both runs the molecules were found to be orientationally disordered.     

A kinetic study of water evolution from a molten hydrated salt

Meso lithium potassium tartrate dihydrate melted before dehydration and a kinetic study of this reaction has been completed. This system is of interest in establishing the kinetic characteristics of a homogeneous rate process in the absence of added solvent. Results are of interest in considering the mechanisms of solid or condensed state reactions where melting is a possibility.The evolution of the initial 1.2H₂O from the single crystal dihydrate reactants was zero order, the rate then became deceleratory and the first order expression was obeyed to 1.6H₂O. The activation energy of the process was high, 230±10 kJ mol^–1 (350–380 K). Evolution of the remaining water occurred by a slower first-order process to give the anhydrous salt. The dehydration of crushed powder reactant was initially relatively more rapid but was deceleratory throughout, obeying the first order equation. It is concluded that salt dehydration is controlled by the rate of surface release of water that is comparatively mobile within the reactant melt.G.M.L. thanks the Department of Education for Northern Ireland for the award of a Postgraduate Scholarship held during this work.