Excitonic splittings in molecular dimers: why static ab initio calculations cannot match them

After decades of research on molecular excitons, only few molecular dimers are available on which exciton and vibronic coupling theories can be rigorously tested. In centrosymmetric H-bonded dimers consisting of identical (hetero)aromatic chromophores, the monomer electronic transition dipole moment vectors subtract or add, yielding S0 → S1 and S0 → S2 transitions that are symmetry-forbidden or -allowed, respectively. Symmetry breaking by 12C/13C or H/D isotopic substitution renders the forbidden transition weakly allowed. The excitonic coupling (Davydov splitting) can then be measured between the S0 → S1 and S0 → S2 vibrationless bands. We discuss the mass-specific excitonic spectra of five H-bonded dimers that are supersonically cooled to a few K and investigated using two-color resonant two-photon ionization spectroscopy. The excitonic splittings Δcalc predicted by ab initio methods are 5–25 times larger than the experimental excitonic splittings Δexp. The purely electronic ab initio splittings need to be reduced (“quenched”), reflecting the coupling of the electronic transition to the optically active vibrations of the monomers. The so-called quenching factors Γ < 1 can be determined from experiment (Γexp) and/or calculation (Γcalc). The vibronically quenched splittings Γ·Δcalc are found to nicely reproduce the experimental exciton splittings.

Ab initio calculations of Ca III Stark broadening parameters,transition probabilities and radiative lifetimes

We have determined matrix elements for all experimental configurations of Ca III, including the 3s3p63d configuration. These values have been obtained using intermediate coupling (IC). For these IC calculations, we have used the standard method of least-squares fitting from the experimental energy levels, using the computer code developed by Robert Cowan. In this paper, using these matrix elements, we report the calculated values of the Ca III Stark widths and shifts for 148 spectral lines, of 56 Ca III spectral line transition probabilities and of eight radiative lifetimes of Ca III levels. The Stark widths and shifts, calculated using the Griem semi-empirical approach, correspond to the spectral lines of Ca III and are presented for an electron density of 1017 cm?3 and temperatures T = 1.0?10.0 (×104 K). The theoretical trends of the Stark broadening parameter versus the temperature are presented for transitions that are of astrophysical interest. There is good agreement between our calculations, for transition probabilities and radiative lifetimes, and the experimental values presented in the literature. We have not been able to find any values for the Stark parameters in the references.

Ab-Initio calculations including Van der Waals interactions: the SnS2 layered material

Tin disulfide SnS2 was recently proposed as a high efficiency solar cell precursor [1]. The aim of this work is a deep study of the structural disposition of the most important polytipes of this layered material, not only describing the electronic correlation but also the interatomic Van der Waals interactions that is present between the layers. The two recent implementations to take Van der Waals interactions into account in the VASP code are the self-consistent Dion et al. [2] functional optimized for solids by Michaelides et al [3] and the Grimme [4] dispersion correction that is applied after each autoconsistent PBE electronic calculation. In this work these two methods are compared with DFT PBE functional. The results we will presented at this Conference, demonstrates the enhancement of the geometric parameters by the use of the Van der Waals interactions in agreement with the experimental values.

Approximate ab initio calculations and the method of molecular fragments

A two stage approach to performing ab initio calculations on medium and large sized molecules is described. The first step is to perform SCF calculations on small molecules or molecular fragments using the OPIT Program. This employs a small basis set of spherical and p-type Gaussian functions. The Gaussian functions can be identified very closely with atomic cores, bond pairs, lone pairs, etc. The position and exponent of any of the Gaussian functions can be varied by OPIT to produce a small but fully optimised basis set. The second stage is the molecular fragments method. As an example of this, Gaussian exponents and distances are taken from an OPIT calculation on ethylene and used unchanged in a single SCF calculation on benzene. Approximate ab initio calculations of this type give much useful information and are often preferable to semi-empirical approaches, since the nature of the approximations involved is much better defined.

Ab initio, DFT and transition state theory calculations on 1,2-HF, HCI and CIF elimination reactions from CH2F-CH2Cl

This paper reports ab intio, DFT and transition state theory (TST) calculations on HF, HCI and CIF elimination reactions from CH2Cl-CH2F molecule. Both the ground state and the transition state for HX elimination reactions have been optimized at HF, MP2 and DFT calculations with 6-31G*, 6-31G** and 6-311++G** basis sets. In addition, CCSD(T) single point calculations were carried out with MP2/6-311++G** optimized geometry for more accurate determination of the energies of the minima and transition state, compared to the other methods employed here. Classical barriers are converted to Arrhenius activation energy by TST calculations for comparisons with experimental results. The pre-exponential factors, A, calculated at all levels of theory are significantly larger than the experimental values. For activation energy, E-a DFT gives good results for HF elimination, within 4-8 W mol(-1) from experimental values. None of the methods employed, including CCSD(T), give comparable results for HCI elimination reactions. However, rate constants calculated by CCSD(T) method are in very good agreement with experiment for HCI elimination and they are in reasonable agreement for HF elimination reactions. Due to the strong correlation between A and E., the rate constants could be fit to a lower A and E-a (as given by experimental fitting, corresponding to a tight TS) or to larger A and E-a (as given by high level ab initio calculations, corresponding to a loose TS). The barrier for CIF elimination is determined to be 607 U mol(-1) at HF level and it is unlikely to be important for CH2FCH2Cl. Results for other CH2X-CH2Y (X,Y = F/Cl) are included for comparison.

Ab initio and tight-binding calculations of noncollinear magnetism in manganese clusters

Combining ab initio and tight-binding calculations, we have studied the noncollinear magnetism in manganese clusters. The oscillations in the per-atom moments observed experimentally are reproduced theoretically. The tendency of antiferromagnetic coupling between near neighbors leads to noncollinear coupling between atoms within the clusters. For clusters containing 12, 13, 15, 19, and 23 atoms, the geometrical structures were optimized from ab initio calculations with collinear coupled spin moments among different atomic sites. For larger clusters such as Mn-36 and Mn-55, the geometries are taken as portions of an fcc structure. Although the local atomic moments have high values close to 4 mu(B), the net moments lie in the range of 0.4-1.2 mu(B)/atom. Taking the noncollinear coupling into account brings the calculated magnetic moments much closer to the experimental results.

The role of V2O5 on the dehydrogenation and hydrogenation in magnesium hydride : An ab initio study

Ab initio density functional theory calculations are performed to study the experimentally observed catalytic role of V2O5 in the recycling of hydrogen in magnesium hydride. We find that the Mg–H bond length becomes elongated when MgH2 clusters are positioned on single, two, and three coordinated oxygen sites (O1, O2, and O3) on the V2O5(001) surface. Molecular hydrogen is predicted to spontaneously form at the hole site on the V2O5(001) surface. Additionally, the activation barrier for the dissociation of hydrogen on V-doped Mg(0001) surface is 0.20 eV, which is only 1/5 of that on pure Mg(0001) surface. Our results indicate that oxygen sites on the V2O5(001)surface and the V dopant in Mg may be important facilitators for dehydrogenation and rehydrogenation, respectively. The understanding gained here will aid in the rational design and development of Mg-based hydrogen storage materials.

Electron capture of tetracyanoethylene oxide in the gas phase. Rearrangement of the parent radical anion to form [(NC)(3)C](-). A joint experimental and ab initio study

Capture of an electron by tetracyanoethylene oxide can initiate a number of decomposition pathways. One of these decompositions yields [(NC)3C]− as the ionic product. Ab initio calculations (at the B3LYP/6-31+G∗ level of theory) indicate that the formation of [(NC)3C]− is initiated by capture of an electron into the LUMO of tetracyanoethylene oxide to yield the anion radical [(NC)2C–O–C(CN)2]−· that undergoes internal nucleophilic substitution to form intermediate [(NC)3C–OCCN]−·. This intermediate dissociates to form [(NC)3C]− (m/z 90) as the ionic product. The radical (NC)3C· has an electron affinity of 4.0 eV (385 kJ mol−1). Ab initio calculations show that [(NC)3C]− is trigonal planar with the negative charge mainly on the nitrogens. A pictorial representation of this structure is the resonance structure formed from three degenerate contributing structures (NC)2–CCN−. The other product of the reaction is nominally (NCCO)·, but there is no definitive experimental evidence to indicate whether this radical survives intact, or decomposes to NC· and CO. The overall process [(NC)2C–O–C(CN)2]−· → [(NC)3C]− + (NCCO)· is calculated to be endothermic by 21 kJ mol−1 with an overall barrier of 268 kJ mol−1.

Use of L matrix to obtain reliable ab initio force constants of polyatomic molecules: ethylene as a test system

Direct use of experimental eigenvalues of the vibrational secular equation on to the ab initio predicted eigenvector space is suggested as a means of obtaining a reliable set of intramolecular force constants. This method which we have termed RECOVES (recovery in the eigenvector space) is computationally simple and free from arbitrariness. The RECOVES force constants, by definition, reproduce the experimental vibrational frequencies of the parent molecule exactly. The ab initio calculations were carried out for ethylene as a test molecule and the force constants obtained by the present procedure also correctly predict the vibrational frequencies of the deuterated species. The RECOVES force constants for ethylene are compared with those obtained by using the SQM procedure.

UVPES and ab initio molecular orbital studies on the electron donor-acceptor complexes of bromine with methylamines

The He I photoelectron spectra of bromine, methylamine, and their complex have been obtained, and the spectra show that lone-pair orbital energy of nitrogen in methylamine is stabilized by 1.8 eV and the bromine orbital energies are destabilized by about 0.5 eV due to complexation. Ab initio calculations have been performed on the charge-transfer complexes of Br-2 with ammonia and methyl-, dimethyl-, and trimethylamines at the 3-21G*, 6-311G, and 6-311G* levels and also with effective core potentials. Calculations predict donor and acceptor orbital energy shifts upon complexation, and there is a reasonable agreement between the calculated and experimental results. Complexation energies have been corrected for BSSE. Frequency analysis has confirmed that ammonia and trimethylamine form complexes with C-3v symmetry and methylamine and dimethylamine with C-s symmetry. Calculations reveal that the lone-pair orbital of nitrogen in amine and the sigma* orbital of Br-2 are involved in the charge-transfer interaction. LANL1DZ basis seems to be consistent and give a reliable estimate of the complexation energy. The computed complexation energies, orbital energy shifts, and natural bond orbital analysis show that the strength of the complex gradually increases from ammonia to trimethylamine.

Thermal decomposition of haloethanols: single pulse shock tube and ab initio studies

This paper reports single pulse shock tube and ab initio studies on thermal decomposition of 2-fluoro and 2-chloroethanol at T=1000–1200 K. Both molecules have HX (X = F/Cl) and H2O molecular elimination channels. The CH3CHO formed by HX elimination is chemically active and undergoes secondary decomposition resulting in the formation of CH4, C2H6, and C2H4. A detailed kinetic simulation indicates that the formation of C2H4 could not be quantitatively explained as arising exclusively from secondary CH3CHO decomposition. Contributions from primary radical processes need to be considered to explain C2H4 quantitatively. Ab initio calculations on HX and H2O elimination reactions from the haloethanols at HF, MP2, and DFT levels with various basis sets up to 6/311++G**are reported. It is pointed out that due to strong correlations between A and Eα, comparison of these two parameters between experimental and theoretical results could be misleading.

Revised ab initio natural band offsets of all group IV, II-VI, and III-V semiconductors

Using an all-electron band structure approach, we have systematically calculated the natural band offsets between all group IV, III-V, and II-VI semiconductor compounds, taking into account the deformation potential of the core states. This revised approach removes assumptions regarding the reference level volume deformation and offers a more reliable prediction of the "natural" unstrained offsets. Comparison is made to experimental work, where a noticeable improvement is found compared to previous methodologies.

Geometries of the Halocarbene anions HCF- and CF2-: ab initio calculation and Franck-Condon analysis

A theoretical method to calculate multidimensional Franck-Condon factors including Duschinsky effects is described and used to simulate the photoelectron spectra of HCF- and CF2- radicals. Geometry optimization and harmonic vibrational frequency calculations have been performed on the (X) over tilde (1)A' state of HCF and (X) over tilde (2)A" state of HCF-, and (X) over tilde (1)A(1) state of CF2 and (X) over tilde B-2(1) state of CF2-. Franck-Condon analyses and spectral simulation were carried out on the first photoelectron band of HCF- and CF2- respectively. The theoretical spectra obtained by employing B3LYP/6-311 + G(2d,p) values are in excellent agreement with the observed ones. In addition, the equilibrium geometry parameters, R(CF) = 0.1475 +/- 0.0005 nm, of the (X) over tilde (2)A" state of HCF-, and r(FC) = 0.1425 +/- 0.0005 nm and angle(FCF) = 100.5 +/- 0.5degrees, of the (X) over tilde B-2(i) state of CF2-, are derived by employing an iterative Franck-Condon analysis procedure in the spectral simulation. (C) 2003 Elsevier B.V. All rights reserved.