ALBERT

All Library Books, journals and Electronic Records Telegrafenberg

feed icon rss

Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 110 (1999), S. 7210-7215 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The nature of the aurophilic interaction is studied by applying local second-order Møller–Plesset perturbation theory (LMP2) on model dimers of [X–Au–PH3]2 (X=H, Cl) type. The possibility to decompose the correlation contribution of the interaction energy in the dimer (A–B) into different excitation classes reveals that the dispersion contribution (A→A′,B→B′) is accompanied by an almost equally important ionic component (A→A′,B→A′), at shorter distances. Double excitations where at least one electron originates from the gold 5d orbitals account for almost 90% of the attraction. Relativistic effects amount to 28% of the binding energy and can be traced to arise almost exclusively from the relativistic expansion of gold d-shells. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 107 (1997), S. 4597-4605 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The water dimer interaction energy and its convergence to the basis set limit was investigated, with electron correlation effects treated at the level of second order Møller-Plesset perturbation theory (MP2). ANO-type and large uncontracted basis sets were used, spreading over a wide range in size; the biggest set included 1046 functions with angular momentum up to (l=7). Core correlation effects were treated accurately by augmenting the original valence basis with extended sets of core polarization functions. The MP2 dimer interaction energy at the basis set limit was determined to −4.94±0.02 kcal/mol, with a contribution due to core correlation of −0.04 kcal/mol. Furthermore, based on some elementary considerations from intermolecular perturbation theory, a simple procedure was devised, which brings the counterpoise corrected interaction energies of moderate basis set calculations closer to the basis set limit. The interaction energies so obtained turned out be surprisingly stable with respect to extensions of the basis set. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 5691-5705 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new implementation of local second-order Møller-Plesset perturbation theory (LMP2) is presented for which asymptotically all computational resources (CPU, memory, and disk) scale only linearly with the molecular size. This is achieved by (i) using orbital domains for each electron pair that are independent of molecular size; (ii) classifying the pairs according to a distance criterion and neglecting very distant pairs; (iii) treating distant pairs by a multipole approximation, and (iv) using efficient prescreening algorithms in the integral transformation. The errors caused by the various approximations are negligible. LMP2 calculations on molecules including up to 500 correlated electrons and over 1500 basis functions in C1 symmetry are reported, all carried out on a single low-cost personal computer. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 103 (1995), S. 6114-6126 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The global and local minima, stationary points, and torsional rearrangement processes of cyclic homodromic (H2O)4 were studied on its four-dimensional torsional intermolecular potential energy surface. Eight different energetically low-lying torsional stationary point structures were found by ab initio theory, and fully structure-optimized at the second-order Møller–Plesset level, using large basis sets. Second-order energies close to the one-particle basis set limit were obtained at these geometries using the explicitly correlated Møller–Plesset method. The effects of higher-order correlation energy terms were investigated by coupled cluster theory, and terms beyond second order were found to cancel in good approximation. The S4 symmetric global minimum has a square and almost planar O...O...O...O arrangement with free O–H bonds alternating "up'' and "down'' relative to this plane, with two isometric versions of this structure. Another torsional conformer with two neighboring up O–H bonds followed by two neighboring down O–H bonds is a local minimum, 0.93 kcal/mol above the global minimum. The four versions of this structure are connected to the global minima via two distinct but almost degenerate first-order torsional saddle points, which occur as two sets of eight isometric versions each, both about 1.24 kcal/mol above the global minimum. Yet another set of eight second-order saddle points lies at 1.38 kcal/mol. The structure with three O–H bonds up and one down is not a stationary point, while the structure with all four O–H bonds on the same side of the plane is a first-order saddle point.The fully planar C4h symmetric structure is a fourth-order stationary point 2.8 kcal/mol above the minimum. The torsional interconversion paths between this multitude of points are complex, and are discussed in three-dimensional spaces of symmetry-adapted torsional coordinates, and also in a network representation. The torsional normal-mode eigenvectors point fairly directly along the torsional interconversion pathways, but the harmonic frequencies are well below the corresponding barriers. Tunneling interconversion between torsional conformers is, hence, less important than for the water trimer. © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 103 (1995), S. 7048-7057 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The ground- and first excited state of s-tetrazine arising from a π*←n excitation (1Ag,1B3u) have been studied using the complete active space (CASSCF) and the second order multiconfiguration perturbation theory (CASPT2) ab initio methods. The focus of this study is on the effect of the electronic excitation on the molecular structure and on those electronic properties which are important to model the solvatochromatic behavior of the molecule in polymer matrices as used in permanent hole burning experiments. Since the accurate computation of excited state molecular properties represents a major challenge for today's numerical quantum chemistry, some technical aspects are also considered. The present study shows that the change in geometry upon electronic excitation is small. This is in partial contradiction with the experimental studies which however disagree among themselves [see K. K. Innes, I. G. Ross, and W. R. Moomaw, J. Mol. Spectrosc. 132, 492 (1988), and R. E. Smalley, L. Wharton, and D. H. Levi, ibid. 66, 375 (1977)]. This study also confirms that the first excited state equilibrium structure is of D2h symmetry. In an earlier theoretical study it was found that the D2h symmetry structure may represent a saddle point rather than a minimum on the excited state potential surface [see A. C. Scheiner and H. F. Schaefer III, J. Chem. Phys. 87, 3539 (1987)]. In the first excited state, we observe an increase of the mean polarizability of s-tetrazine along with an enhanced anisotropy. The change in the polarizability is almost exclusively in the "in-plane'' components of the tensor; the polarizability in the vertical direction is nearly unchanged. This observation questions recent experimental results reported for this molecule [see S. Heitz, D. Weidnauer, and A. Hese, J. Chem. Phys. 95, 7952 (1991)]. © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 103 (1995), S. 6350-6361 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report a combined spectroscopic and theoretical investigation of the intermolecular vibrations of supersonic jet-cooled phenol⋅(H2O)3 and d1-phenol⋅(D2O)3 in the S0 and S1 electronic states. Two-color resonant two-photon ionization combined with time-of-flight mass spectrometry and dispersed fluorescence emission spectroscopy provided mass-selective vibronic spectra of both isotopomers in both electronic states. In the S0 state, eleven low-frequency intermolecular modes were observed for phenol⋅(H2O)3, and seven for the D isotopomer. For the S1 state, several intermolecular vibrational excitations were observed in addition to those previously reported. Ab initio calculations of the cyclic homodromic isomer of phenol⋅(H2O)3 were performed at the Hartree–Fock level. Calculations for the eight possible conformers differing in the position of the "free'' O–H bonds with respect to the almost planar H-bonded ring predict that the "up–down–up–down'' conformer is differentially most stable. The calculated structure, rotational constants, normal-mode eigenvectors, and harmonic frequencies are reported. Combination of theory and experiment allowed an analysis and interpretation of the experimental S0 state vibrational frequencies and isotope shifts. © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 100 (1994), S. 1780-1780 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 114 (2001), S. 661-681 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new implementation of local coupled-cluster theory with single and double excitations (LCCSD) is presented for which asymptotically all computational resources (CPU, memory, and disk) scale only linearly with the molecular size. This is achieved by: (i) restricting the correlation space for each electron pair to domains that are independent of molecular size; (ii) classifying the pairs according to a distance criterion and treating only strong pairs at the highest level; (iii) using efficient prescreening algorithms in the integral transformation and other integral-direct procedures; and (iv) neglect of small couplings of electron pairs that are far apart from each other. The errors caused by the various approximations are negligible. LCCSD calculations on molecules including up to 300 correlated electrons and over 1000 basis functions in C1 symmetry are reported, all carried out on a workstation. © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 5228-5238 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The minimum energy structure of the cyclic water trimer, its stationary points, and rearrangement processes at energies 〈1 kcal/mol above the global minimum are examined by ab initio molecular orbital theory. Structures corresponding to stationary points are fully optimized at the Hartree–Fock and second-order Møller–Plesset levels, using the 6-311++G(d,p) basis; each stationary point is characterized by harmonic vibrational analyses. The lowest energy conformation has two free O–H bonds on one and the third O–H bond on the other side of an approximately equilateral hydrogen-bonded O...O...O (O3) triangle. The lowest energy rearrangement pathway corresponds to the flipping of one of the two free O–H bonds which are on the same side of the plane across this plane via a transition structure with this O–H bond almost within the O3 plane. Six distinguishable, but isometric transition structures of this type connect six isometric minimum energy structures along a cyclic vibrational-tunneling path; neighboring minima correspond to enantiomers. The potential energy along this path has C6 symmetry and a very low barrier V6=0.1±0.1 kcal/mol. This implies nearly free pseudorotational interconversion of the six equilibrium structures. The corresponding anharmonic level structure was modeled using an internal rotation Hamiltonian. Two further low-energy saddle points on the surface are of second and third order; they correspond to crown-type and planar geometries with C3 and C3h symmetries, respectively. Interconversion tunneling vibrations via these stationary points are also important for the water trimer dynamics. A unified and symmetry-adapted description of the intermolecular potential energy surface is given in terms of the three flipping coordinates of the O–H bonds. Implications of these results for the interpretation of spectroscopic data are discussed.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 3763-3776 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Extensive ab initio calculations of the phenol⋅H2O complex were performed at the Hartree–Fock level, using the 6-31G(d,p) and 6-311++G(d,p) basis sets. Fully energy-minimized geometries were obtained for (a) the equilibrium structure, which has a translinear H bond and the H2O plane orthogonal to the phenol plane, similar to (H2O)2; (b) the lowest-energy transition state structure, which is nonplanar (C1 symmetry) and has the H2O moiety rotated by ±90°. The calculated MP2/6-311G++(d,p) binding energy including basis set superposition error corrections is 6.08 kcal/mol; the barrier for internal rotation around the H bond is only 0.4 kcal/mol. Intra- and intermolecular harmonic vibrational frequencies were calculated for a number of different isotopomers of phenol⋅H2O. Anharmonic intermolecular vibrational frequencies were computed for several intermolecular vibrations; anharmonic corrections are very large for the β2 intermolecular wag. Furthermore, the H2O torsion τ around the H-bond axis, and the β2 mode are strongly anharmonically coupled, and a two-dimensional τ/β2 potential energy surface was explored. The role of tunneling splitting due to the torsional mode is discussed and tunnel splittings are estimated for the calculated range of barriers. The theoretical studies were complemented by a detailed spectroscopic study of h-phenol⋅H2O and d-phenol⋅D2O employing two-color resonance-two-photon ionization and dispersed fluorescence emission techniques, which extends earlier spectroscopic studies of this system. The β1 and β2 wags of both isotopomers in the S0 and S1 electronic states are newly assigned, as well as several other weaker transitions. Tunneling splittings due to the torsional mode may be important in the S0 state in conjunction with the excitation of the intermolecular σ and β2 modes.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...