Polaronic Mechanism of Vibronic Localization in Mixed-Valence Cation Radicals with a Non-Conjugated Chromophore on the Bridge.

In quest of a controllable intramolecular electron transfer (ET) across a bridge, we study the cation-radical form of the parent 1,4-diallyl-butane (I) and its derivatives (II)-(VI). In these mixed-valence (MV) compounds, the bridge of variable length connecting allyl redox sites can be either saturated (-CH2 CH2-) (I, III, and V) or unsaturated, modified by the π-spacer (-HC═CH-) (II, IV, and VI). Ab initio calculations for the charge delocalized transition structure and for fully optimized localized form of 1,ω-diallyl cation radicals I-VI allowed us to estimate the potential barriers for ET between the terminal allyl groups, vibronic coupling, and ET parameters. The ET barrier in all compounds with the π-fragment on the bridge is shown to be higher with respect to that in the systems with a saturated bridge. We propose a model based on the concept of a specific polaronic effect of the spacer. Charge localization at an allyl group creates an electric field polarizing the π-fragment and the bridge as a whole. The induced dipole moment interacts with the localized charge giving rise to the additional vibronic stabilization in a self-consistent manner without an appreciable change of localized charge. Utilization of this spacer-driven polaronic effect is expected to provide a route to a controllable ET in bridged MV compounds.

Mixed-Valence Bridged Norbornylogous Compounds as Switchable Cells for Molecular Quantum Cellular Automata: A Compromise between High Polarizability and Low Power Dissipation.

In this article, we analyze power dissipation in the nonadiabatic switching event in mixed-valence (MV) molecular cells of quantum cellular automata (QCA) in combination with a key functional property of cells such as polarizability in the applied electric field. We demonstrate that although the requirements for a strong nonlinear response of the cell to the applied electric field and low heat release are competing from the point of view of molecular parameters, this by no means can be regarded as an insurmountable obstacle for achieving functional advantages and possibility of practical application of QCA. The general theoretical consideration is applied to the series of MV compounds exemplifying electric field-switchable MV molecules, which include oxidized norbornadiene [C7H8]+ (I) and its polycyclic derivatives [C12H12]+ (II), [C17H16]+, (III), [C27H24]+ (IV), and [C32H28]+ (V). Based on the results of high-level ab initio calculations performed for the series of compounds with variable length of the bridge connecting redox groups, we show that strongly localized cation radicals with long bridges can be easily polarized even by a fairly weak electric field. This ensures quite low power dissipation, which is shown to coexist with a rather strong nonlinear cell-cell response. We thus conclude that consideration of the series of MV dimers with controllable electron transfer provides a reasonable way to design molecule-based QCA cells with the required properties.

Spin polarization effects in trigonal mixed-valence complexes exhibiting double exchange supported by external spin-cores.

The theory of the magnetic coupling between the localized spins, mediated by the mobile excess electron, is generalized to the case of a trigonal, six-center, four-electron molecule with partial valence delocalization. The combination of the electron transfer occurring within the valence-delocalized subsystem and the interatomic exchange producing coupling of the spin of the mobile electron of valence-delocalized fragment with the three localized spins forming the valence-localized subsystem leads to the appearance of a special kind of double exchange (DE), termed the "external core double exchange" (ECDE), in order to distinguish such DE from the conventional "internal core double exchange" for which the mobile electron is coupled with the spin-cores on the same center via the intra-atomic exchange. The effect of the ECDE on the ground spin state of the considered trigonal molecule is compared with earlier reported effect produced by DE in the four-electron, mixed-valence (MV) trimer. A high diversity of the ground spin states is revealed, depending on the relative magnitudes and signs of the electron transfer and interatomic exchange parameters, with part of these states not appearing to be the ground states in a trigonal trimer exhibiting DE. We briefly discuss some examples of trigonal MV systems from the point of view of the possibility to have different combinations of signs of the transfer and exchange parameters and, accordingly, different ground spin states. The tentative role of the considered systems in molecular electronics and spintronics is also noticed.

Controllable Electron Transfer in Mixed-Valence Bridged Norbornylogous Compounds: Ab Initio Calculation Combined with a Parametric Model and Through-Bond and Through-Space Interpretation.

In the context of a computationally guided approach to the controllable electron transfer in mixed-valence (MV) systems, in this article, we study the electron transfer (ET) in the series of oxidized norbornadiene C7H8 (I) and its polycyclic derivatives, C12H12 (II), C17H16, (III), C27H24 (IV), and C32H28 (V), with variable lengths of the bridge connecting redox sites. The work combines an ab initio CASSCF evaluation of the electronic structure of systems I-V with the parametric description in the framework of the biorbital two-mode vibronic model. The model involves coupling with the "breathing" mode and intercenter vibration modulating the distances between the redox fragments. The ab initio calculations were performed for two types of optimized structures of I-V: (a) charge-localized global minimum (Cs) and (b) symmetric configuration (C2v) with the delocalized charge. This allows one to estimate the potential barrier separating charge-localized configurations as well as vibronic coupling parameters and the electron transfer integral. Along with the adiabatic approach, the quantum-mechanical analysis of the vibronic levels has been applied to precisely estimate the quantum effect of tunneling splitting. We estimate the "through-space" and "through-bond" contributions to the parameters interrelated with the charge transfer (CT). The through-space effect proves to be a major factor of ET at a short distance between the redox centers, whereas the through-bond contribution is dominant at a long distance. Vibronic coupling under the condition of through-space ET leads to the localization of the positive charge on the π-chromophore, while the through-bond component of ET results in compensating σ-shifts and subsequent charge delocalization over the bridge. The limitations of the parametric approach were discussed in the context of the two components contributing to the ET. Particularly, the bridge polarization in the course of through-bond ET proves to be beyond the basis of the employed parametric model.

Vibronic recovering of functionality of quantum cellular automata based on bi-dimeric square cells with violated condition of strong Coulomb repulsion.

Strong Coulomb repulsion between the two charges in a square planar mixed-valence cell in quantum cellular automata (QCA) allows us to encode the binary information in the two energetically beneficial diagonal distributions of the electronic density. In this article, we pose a question: to what extent is this condition obligatory for the design of the molecular cell? To answer this question, we examine the ability to use a square-planar cell composed of one-electron mixed valence dimers to function in QCA in a general case when the intracell Coulomb interaction U is not supposed to be extremely strong, which means that it is comparable with the characteristic electron transfer energy (violated strong U limit). Using the two-mode vibronic model treated within the semiclassical (adiabatic) and quantum-mechanical approaches, we demonstrate that strong vibronic coupling is able to create a considerable barrier between the two diagonal-type charge configurations, thus ensuring bistability and polarizability of the cells even if the Coulomb barrier is not sufficient. The cases of weak and moderate Coulomb repulsion and strong vibronic coupling are exemplified by consideration of the cation radicals of the two polycyclic derivatives of norbornadiene [C12H12]+ and [C17H16]+ with the terminal C=C chromophores playing the role of redox sites. By using the detailed ab initio data, we reveal the main characteristics of the bi-dimeric cells composed of these molecules and illustrate the pronounced effect of the vibronic recovery clearly manifesting itself in the shape of the cell-cell response function. Revealing such "vibronic recovery" of strong localization when the strong U limit is violated suggests a way to a significant expansion of the class of molecular systems suitable as QCA cells.

Insight Into The Spin-Vibronic Problem of a Mixed Valence Magnetic Molecular Cell for Quantum Cellular Automata.

The effects of the vibronic coupling in quantum cellular automata (QCA) based on the square planar mixed valence (MV) molecular cells comprising four paramagnetic centers (spin cores) and two excess mobile electrons are analyzed in the important particular case when the Coulomb energy gap between the ground antipodal diagonal-type two-electron configurations and the excited side-type configurations considerably exceeds both the one-electron transfer parameter (strong U-limit) and the vibronic stabilization energy. Under such conditions the developed model involves the second-order double exchange, the Heisenberg-Dirac-Van Vleck (HDVV) exchange and the vibronic coupling of the excess electrons with the molecular B1g -vibration composed of four full-symmetric local vibrations. The latter interaction is shown to significant amplify the ability of the electric field produced by the driver-cell to polarize the excess electrons in the working cell, which can be termed "the effect of the vibronic enhancement of the cell-cell interaction". This effect leads to a redetermination of the conditions for switching between different spin-states, as well as to a significant change in the shapes of the cell-cell response functions. The obtained results demonstrate the importance of the vibronic coupling in all aspects (such as description of a free cell and cell-cell response) of the theory of molecular QCA based on MV clusters.

In Search of the Perfect Triple BB Bond: Mechanical Tuning of the Host Molecular Trap for the Triple Bond B≡B Fragment.

The coordination of the B2 fragment by two σ-donor ligands L: could lead to a diboryne compound with a formal triple bond L:→B≡B←:L. σ-Type coordination L:→B leads to an excess of electrons around the B2 central fragment, whereas π-back-donation from the B≡B moiety to ligand L has a compensation effect. Coordination of the σ-donor and π-acceptor ligand is accompanied by the lowering of the BB bond order. Here, we propose a new approach to obtain the perfect triple BB bond through the incorporation of the BB unit into a rigid molecular capsule. The idea is the replacement of π-back-donation, as the principal stabilization factor in the linear NBBN structure, with the mechanical stabilization of the BB fragment in the inert molecular capsule, thus preserving the perfect B≡B triple bond. Quantum-chemical calculations show that the rigid molecular capsule provided a linear NBBN structure and an unusually short BB bond of 1.36 Å. Quantum-chemical calculations of the proposed diboryne adducts show a perfect triple bond B≡B without π-back-donation from the B2 unit to the host molecule. Two mechanisms were tested for the molecular design of a diboryne adduct with a perfect B≡B triple bond: the elimination of π-back-donation and the construction of a suitable molecular trap for the encapsulation of the B2 unit. The second factor that could lead to the strengthening or stretching of a selected chemical bond is molecular strain produced by the rigid molecular host capsule, as was shown for B≡B and for C≡C triple bonds. Different derivatives of icosane host molecules exhibited variation in BB bond length and the corresponding frequency of the BB stretch. On the other hand, this group of molecules shows a perfect triple BB bond character and they all possess a similar level of HOMO.

A parametric two-mode vibronic model of a dimeric mixed-valence cell for molecular quantum cellular automata and computational ab initio verification.

In this article we propose a two-mode vibronic model of a molecular cell for quantum cellular automata. The molecular cell is represented by a mixed-valence dimeric cluster in which the mobile electron is coupled to two kinds of molecular vibrations. The first type of vibration is represented by the so-called "breathing" modes localized on the redox sites, which are traditionally considered within the Piepho, Krausz and Schatz vibronic model as a source of the trapping effect. The second type includes the "intercenter" vibration, which changes the distance between the redox centers enhancing thus the degree of delocalization in the bonding orbital of the cell. The cell-cell response function as a key characteristic of the cell is evaluated in the framework of the dynamic (quantum-mechanical) solution of the two-mode vibronic problem. To elucidate the physical sense of precise quantum-mechanical results, a more imaginative semiclassical (adiabatic) picture is used. Competitive effects of the two kinds of active vibrations on the cell-cell response function are analyzed and the conditions are established under which a mixed-valence dimer can work as a functioning molecular cell in a quantum cellular automation device. One of the aims of this article was to combine the parametric approach that gives a very common description (that allows the qualitative comparison of properties in a series of compounds) with the ab initio evaluations providing numerical estimations of the parameters involved in the semiempirical approach for a real molecule. Along with the parametric approach the quantum-chemical modelling is used for investigating the cation-radical of the tetramethyleneethane molecule which was shown to belong to the class of strongly delocalized systems. It was demonstrated that an efficient control over the electronic and vibronic parameters can be achieved through the design of its derivatives through a spacer interposed between the two allyl fragments. The strongly conjugated C[double bond, length as m-dash]C spacer was shown to partially block the channel mediating electronic communication so that the molecule becomes strongly localized. The interconnection between the parametric and ab initio approaches is established.

Carbonate and carbonate anion radicals in aqueous solutions exist as CO3(H2O)62- and CO3(H2O)6˙- respectively: the crucial role of the inner hydration sphere of anions in explaining their properties.

An effort to reproduce the chemical and physical properties of carbonate and carbonate anion radicals in aqueous solutions by DFT proves that one has to include an inner hydration sphere of six water molecules for both anions. Application of the SMD model to CO3(H2O)62- and CO3(H2O)6˙- enables achievement of the experimental value of the redox potential of the CO3(H2O)6˙-/2- couple. This is a result of the direct inclusion of a considerable charge transfer (CT) from CO32- to its inner hydration sphere in the calculation of the hydration effect. The HOMO of clusters is an analogue of the non-bonding σ-type a2'-HOMO of the parent CO3 moiety with a σ*(OH) contribution. This is a MO manifestation of the CT to the first hydration shell. The localization of the CT on the first hydration shell also re-produces the very strong OHO stretch peak. Furthermore, the very large difference in the hydration energies of CO32- and CO3˙- which causes the very large differences in the length of the C-OH-O hydrogen bonds suggests that the oxidations by CO3˙- proceed via the inner sphere mechanism.

Less stable tautomers form stronger hydrogen bonds: the case of water complexes.

Hydrogen bonding in cyclic complexes of water with tautomeric pairs of molecules M0 and M1 is calculated to be stronger by more than 25% for the less stable tautomer M1 in all cases where the energy gap between the two tautomers is large (ΔE(M0 - M1) > 10 kcal mol-1). This is accompanied by a large red-shift (>200 cm-1) of the N-H/O-H stretch frequency in the complexes involving M1. Large barriers for double proton transfer in both directions should permit an experimental verification. Exceptions to this rule were found in heterocycles with an N-C[double bond, length as m-dash]O fragment incorporated into a conjugated cycle resulting in two nearly degenerate tautomers - keto and enol forms. The wavefunction of the keto form has a large contribution from a zwitterionic VB structure which is also aromatic. This increases the polarity of the keto group, making the oxygen atom a strong H-bond acceptor. It can also stabilize the keto form below the aromatic enol form. In this case the extra-HB stabilization is observed for the most stable tautomer (i.e. for the keto form). H-bonding enhances the aromatic character of less aromatic molecules, but the more aromatic tautomers partially loose aromaticity.

Origin of the Regioselectivity in the Gas-Phase Aniline+CH3 (+) Electrophilic Aromatic Substitution.

Nonadiabatic ab initio molecular dynamics simulations are carried out to monitor the attack of CH3 (+) on aniline in the gas phase to form the corresponding σ complexes. The reaction is ultrafast and is governed by a single electron transfer within 30 fs, which involves two sequential conical intersections and finally produces a radical pair. Positive-charge allocation in the aromatic compound is found to govern the substitution pattern in ortho, meta, or para position. Although the major products in the first step of the electrophilic aromatic substitution are the ortho and para σ complexes, initially 26 % of the simulated trajectories also form meta complexes, which then undergo H shifts, mainly to the para position.

Gas-phase electrophilic aromatic substitution mechanism with strong electrophiles explained by ab initio non-adiabatic dynamics.

Ab initio non-adiabatic dynamics is used to monitor the attack of CH3(+) to benzene. The results show that in the gas phase the reaction is ultrafast and is governed by a single electron transfer producing a radical pair.

The photo-dissociation of the pyrrole-ammonia complex--the role of hydrogen bonding in Rydberg states photochemistry.

The photochemistry of the pyrrole-ammonia cluster is analyzed theoretically. Whereas in neat pyrrole the dominant photochemical reaction is H-atom cleavage, recent experiments show that in pyrrole-ammonia clusters the major reaction is H-transfer to form the NH(4) radical (solvated by ammonia molecules in the case of large clusters) and the pyrrolyl radical. A mechanism involving the hydrogen-bonded Rydberg state is offered to account for these results and verified computationally. Two minima are located on the lowest excited singlet PES. Both of them are Rydberg states, one leads to the formation of NH(4) and pyrrolyl radicals, the other is connected to the πσ* state through a relatively high barrier, leading to a 3-body dissociation reaction to form a pyrrolyl radical, ammonia and an H-atom. The former is the energetically and statistically preferred one.

Role of Rydberg states in the photostability of heterocyclic dimers: the case of pyrazole dimer.

A new route for the nonradiative decay of photoexcited, H-bonded, nitrogen-containing, heterocyclic dimers is offered and exemplified by a study of the pyrazole dimer. In some of these systems the N(3s) Rydberg state is the lowest excited singlet state. This state is formed by direct light absorption or by nonradiative transition from the allowed ππ* state. An isomer of this Rydberg state is formed by H atom transfer to the other component of the dimer. The newly formed H-bonded radical pair is composed of two radicals (a H-adduct of pyrazole, a heterocyclic analogue of the NH(4) radical) and the pyrazolium π-radical. It is calculated to have a shallow local minimum and is the lowest point on the PES of the H-pyrazole/pyrazolium radical pair. This species can cross back to the ground state of the original dimer through a relatively small energy gap and compete with the H-atom loss channel, known for the monomer. In both Rydberg dimers, an electron occupies a Rydberg orbital centered mostly on one of the two components of the dimer. This Rydberg Center Shift (RCS) mechanism, proposed earlier (Zilberg, S.; Kahan, A.; Haas, Y. Phys. Chem. Chem. Phys. 2012, 14, 8836), leads to deactivation of the electronically excited dimer while keeping it intact. It, thus, may explain the high photostability of the pyrazole dimer as well as other heterocyclic dimers.

Towards experimental determination of conical intersection properties: a twin state based comparison with bound excited states.

The energy and approximate structure of certain S(0)/S(1) conical intersections (CI) are shown computationally to be deducible from those of two bound states: the first triplet (T(1)), which is iso-energetic with the CI, and the second excited singlet state (S(2)). This is demonstrated for acepentalene (I) and its perfluoro derivative (II) using the twin state concept for three states systems and based on the fact that the triplet T(1) is almost degenerate with the CI. The stable S(2) (C(3v) configuration) state exhibits unusual exaltation of Jahn-Teller active degenerate mode-ν(JT) = 2058 cm(-1) (∼500 cm(-1) higher than analogous e-mode of the symmetric (C(3v)) T(1) and the dianion I(-2) or any C-C vibration of the Jahn-Teller distorted (C(s)) ground state minimum). The acepentalene molecule, whose rigid structure and possibility to attain the relatively high symmetry C(3v) configuration, is a particularly suitable candidate for this purpose.

Frequency upshift in BO2 and CO2+ upon electronic excitation: a twin-state model rationalization.

The twin-state model, previously shown to provide a simple physical rationalization for the frequency upshift (exaltation) of the Kekulé mode in benzene upon S(0) to S(1) electronic excitation, is extended to the case of the BO(2) radical and the CO(2)(+) radical cation. In the case of BO(2)/CO(2)(+), the ground and excited states are degenerate, yet the model applies to the degenerate two-state system as well. In contrast with a pseudo-Jahn-Teller model, the twin-state one can predict which frequency is exalted and also which pair of electronic states are coupled, thus explaining the specificity of the phenomenon. The frequency exaltation is a spectroscopic manifestation of the resonance between the pair of VB structures describing twin states. In analogy with the case of benzene, it is predicted that the ν(3) asymmetric stretch fundamental will be a dominant peak in the two-photon absorption spectrum of BO(2) and CO(2)(+).

Solvent tuning of a conical intersection: direct experimental verification of a theoretical prediction.

We report an ultrafast study of a merocyanine molecule, whose fluorescence lifetime was tuned by changing the solvent's polarity. A recent theoretical prediction that the fluorescence lifetime is considerably shortened upon lowering the polarity of the solvent, due to tuning of the conical intersection properties, is fully confirmed (Xu et al. J. Phys. Chem. A 2009, 113, 9779-9791). This constitutes a direct measurement of a previously predicted tunable property of a conical intersection.

Electronic structure of 9-mesityl-10-methylacridinium in ground and excited states: charge-shift mechanism introduced by counter anion shift.

The origin of the lowest triplet states--locally excited or charge shifted (T(LE)vs. T(CS))--is a key point in the discussion of the charge shift phenomena of 9-mesityl-10-methylacridinium (see Fukuzumi et al. Phys. Chem. Chem. Phys., 2008, 10, 5159 vs. Benniston et al., Phys. Chem. Chem. Phys., 2008, 10, 5156). Coordination of the anion on the mesityl moiety provides the effective stabilization of the charge-shifted state.

Long-Range N-N Bonding by Rydberg Electrons.

By using high-level ab initio methods, we examine the nature of bonding between Rydberg electrons hosted by two four-coordinate nitrogen centers embedded in a hydrocarbon scaffold. The electronic structure of these species resembles that of diradicals, yet the diffuse nature of the orbitals hosting the unpaired electrons results in unusual features. The unpaired Rydberg electrons exhibit long-range bonding interactions, leading to stabilization of the singlet state (relative to the triplet) and a reduced number of effectively unpaired electrons. However, thermochemical gains due to through-space bonding are offset by strong Coulomb repulsion between positively charged nitrogen cores. The kinetic stability of these Rydberg diradicals may be controlled by a judicious choice of the molecular scaffold, suggesting possible strategies for their experimental characterization.

Stability of polynitrogen compounds: the importance of separating the sigma and pi electron systems.

Planar N(x) systems such as cyclo-N(5)(-) and N(5)(+) tend to be more stable than nonplanar systems such as the neutral cyclo-N(6). It is proposed that the key to stabilization is the separation of the sigma and pi electron systems. In both cyclo-N(5)(-) and N(5)(+), a six-pi-electron system is created upon either adding to or removing from the cyclo-N(5) radical one electron. Judicious addition of oxygen atoms to polynitrogen ring compounds such as cyclo-N(4) and cyclo-N(6) can increase their thermodynamic and kinetic stabilities, accompanied by only a small reduction in their efficiency as high energy density materials (HEDMs). The properties of some of these compounds are calculated and compared with the parent all-nitrogen compounds. Coordination of one or more oxygen atoms to the ring leads to effective separation of the sigma and pi electron systems helping to stabilize the systems. Natural bond analysis indicates that the exocyclic NO bonds can assume a single or double bond character, depending on the ring system.