Inverse isotope effects and electron-phonon coupling in the positively charged deutero- and fluoroacenes

Electron-phonon interactions in the monocations of deutero- and fluoroacenes are studied and compared with those in the monocations of acenes and those in the monoanions of fluoroacenes. Because of the significant phase pattern difference between the highest occupied molecular orbitals (HOMO) and the lowest unoccupied molecular orbitals (LUMO), the frequency modes lower than 500 cm(-1) and the high-frequency modes around 1400 cm(-1) couple more strongly to the LUMO than to the HOMO, while the frequency modes around 500 cm(-1) and the frequency modes around 1600 cm(-1) couple more strongly to the HOMO than to the LUMO in fluoroacenes with D2h geometry. The total electron-phonon coupling constants for the monocations (l(HOMO)) are estimated and compared with those for the monoanions (l(LUMO)) in deutero- and fluoroacenes. The l(HOMO) values are estimated to be 0.418, 0.399, 0.301, 0.255, and 0.222 eV for C6F6 (1f), C10F8 (2f), C14F10 (3f), C18F12 (4f), and C22F14 (5f), respectively. The l(HOMO) values are smaller than the l(LUMO) values in small fluoroacenes. But the l(HOMO) value decreases with an increase in molecular size less rapidly than the l(LUMO) value in fluoroacenes, and the l(HOMO) value of 0.074 eV is much larger than the l(LUMO) value of 0.009 eV in polyfluoroacene. The logarithmically averaged phonon frequencies for the monocations (omega(ln,HOMO)) are estimated to be larger than those for the monoanions (omega(ln,LUMO)) in fluoroacenes. This is because the C-C stretching modes around 1600 cm(-1) couple most strongly to the HOMO, and those around 1400 cm(-1) couple the most strongly to the LUMO in fluoroacenes. The significant phase pattern difference between the HOMO and the LUMO is the main reason for the calculational results. The l(HOMO) values increase much more significantly by H-F substitution than by H-D substitution in acenes. The possible inverse isotope effects in the electron-phonon interactions as a consequence of deuteration in the monocations of nanosized molecules are suggested.     

Electron-phonon interactions in photoinduced excited electronic states in fluoroacenes

The electron-phonon coupling constants [l(B1u(HOMO-->LUMO))] in the photoinduced excited electronic states in fluoroacenes are estimated and compared with those in the monoanions (l(LUMO)) and cations (l(HOMO)). The l(B1u(HOMO-->LUMO)) values are much larger than the l(LUMO) and l(HOMO) values in fluoroacenes. Furthermore, the Coulomb pseudopotential mu* values for the excited electronic states are estimated to be smaller than those for the monoanions and cations. The complete phase patterns difference between the highest occupied molecular orbitals (HOMOs) and the lowest unoccupied molecular orbitals (LUMOs) is the main reason why the electron-phonon coupling constants and the mu* values are larger and smaller, respectively, in the photoinduced excited electronic states than in the monoanions and cations. The possible electron pairing and Bose-Einstein condensation in the excited electronic states of fluoroacenes are discussed. Because of larger electron-phonon coupling constants and smaller mu* values in the excited electronic states than in the charged states, the conditions under which the electron-electron interactions become attractive can be more easily realized, in principle, in the excited electronic states than in the charged states in fluoroacenes. The l(B1u(HOMO-->LUMO)) values hardly change by H-F substitution, even though the l(LUMO) and l(HOMO) values significantly increase by H-F substitution in acenes. Antibonding interactions between carbon and fluorine atoms in the HOMO and LUMO are the main reason why the l(B1u(HOMO-->LUMO)) values hardly change by H-F substitution in acenes.     

The essential role of H-F substitution in the electron-phonon interactions and electron transfer in the negatively charged acenes

The single charge transfer through acenes, partially H-F substituted acenes, and fluoroacenes is discussed. The reorganization energies between the neutral molecules and the corresponding monoanions for partially H-F substituted acenes lie between those for acenes and fluoroacenes. The delocalization of the lowest unoccupied molecular orbitals (LUMO) by substituting hydrogen atoms by fluorine atoms with the highest electronegativity in every element is the main reason why the reorganization energy between the neutral molecule and the monoanion for partially H-F substituted acenes lies between those for acenes and fluoroacenes. This result implies that the negatively charged partially H-F substituted acenes would be better conductors with rapid electron transfer than the negatively charged fluoroacenes if we assume that the overlap of the LUMO between partially H-F substituted acenes is not significantly different from that between two neighboring fluoroacenes. The structures of the monoanions of acenes, fluoroacenes, and partially H-F substituted acenes are optimized under D2h geometry, and the Jahn-Teller effects in the monoanions of benzene and fluorobenzene are discussed. The vibration effect onto the charge transfer problem is also discussed. The C-C stretching modes around 1500 cm(-1) are the main modes converting the neutral molecules to the monoanions in acenes, fluoroacenes, and partially H-F substituted acenes. It can be confirmed from the calculational results that the C-C stretching modes around 1500 cm(-1) the most strongly couple to the LUMO in these molecules. The main reason why the total electron-phonon coupling constants (lLUMO) for the monoanions of acenes in which four outer hydrogen atoms are substituted by fluorine atoms are larger than those for the monoanions of acenes in which several inner hydrogen atoms are substituted by fluorine atoms is suggested. The relationships between the electron transfer and the electron-phonon interactions are discussed. The plot of the reorganization energies against the lLUMO values is found to be nearly linear. In view of these results, the relationships between the normal and superconducting states are briefly discussed.     

Electron-phonon interactions in charged cubic fluorocarbon cluster, (CF)8

Electron-phonon interactions in the charged cubic fluorocarbon, (CF)8 are studied, and compared with those in charged (CH)8 and (CD)8. The A1g mode of 1470 cm(-1) much more strongly couples to the a1g lowest unoccupied molecular orbitals (LUMO) than the A1g mode of 554 cm(-1) in (CF)8. The T2g mode of 1030 cm(-1), the Eg mode of 980 cm(-1), and the A1g mode of 1470 cm(-1) strongly couple to the t2u highest occupied molecular orbitals (HOMO) in (CF)8. The total electron-phonon coupling constants for the monoanion (l(-1)) and monocation (l(+1)) of (CF)8 are estimated to be 0.932 and 0.585 eV, respectively. The logarithmically averaged phonon frequencies for the monoanion (omega(ln,-1)) and monocation (omega(ln,+1)) of (CF)8 are estimated to be 1365 and 998 cm(-1), respectively. The l(-1) and omega(ln,-1) values increase much more significantly by H-F substitution than by H-D substitution in cubane. The larger displacements of carbon atoms in the high frequency vibronic active mode in (CF)8 than those in (CD)8 due to larger atomic mass of fluorine than that of deuterium, and the unchanged electron distributions in the LUMO somewhat localized on carbon atoms as a consequence of H-F and H-D substitution in cubane, are the main reason why the l(-1) and omega(ln,-1) values increase much more significantly by H-F substitution than by H-D substitution. The l(+1) and omega(ln,+1) values less significantly change than the l(-1) and omega(ln,-1) values by H-F substitution as well as by H-D substitution in cubane. This is because the t2u HOMO in (CF)8 and the t2g HOMO in (CH)8 are somewhat localized on fluorine atoms, and thus, the high frequency vibronic active modes in which the displacements of carbon atoms are large cannot necessarily very strongly couple to the HOMO somewhat localized on fluorine atoms in (CF)8.     

Vibronic interactions in negatively charged polyacetylene

Electron-phonon interactions in the monoanions of polyacetylenes such as C2H4 (2tpa), C4H6 (4tpa), C6H8 (6tpa), and C8H10 (8tpa) are studied and compared with those in the monoanions of polyacenes. The C-C stretching A(g) modes around 1500 cm(-1) the most strongly couple to the lowest unoccupied molecular orbitals (LUMO) in polyacetylenes. The estimated total electron-phonon coupling constants for the monoanions (l(LUMO)) are 0.579, 0.555, 0.463, and 0.401 eV for 2tpa, 4tpa, 6tpa, and 8tpa, respectively. The l(LUMO) values for polyacetylenes are much larger than those for polyacenes. Furthermore, the l(LUMO) value for polyacetylene with C(2h) geometry is estimated to be 0.254 eV, and is larger than that (0.024 eV) for polyacene with D(2h) geometry. The phase patterns difference between the LUMO of polyacenes localized on the edge part of carbon atoms, and the delocalized LUMO of polyacetylenes is the main reason for the calculated results. The single charge transfer through the molecule in polyacetylenes are also discussed. The reorganization energies between the neutral molecule and the corresponding monoanion are estimated to be 0.164, 0.144, 0.125, and 0.113 eV for 2tpa, 4tpa, 6tpa, and 8tpa, respectively. Such reorganization energy decreases with an increase in molecular size. The conditions under which the attractive electron-electron interactions are realized in the monoanions of polyacetylenes and polyacenes are discussed. In terms of the electron-phonon interactions and the reorganization energies, the relationships between the normal and possible superconducting states are briefly discussed. We find that the monoanions with smaller molecular size cannot easily become good conductors, however, the conditions under which the interactions between two electrons are attractive are more easily realized in the monoanions with smaller molecular size than in the monoanions with larger molecular size.     

Vibronic interactions and possible electron pairing in the photoinduced excited electronic States in molecular systems: a theoretical study

Electron-phonon interactions in the photoinduced excited electronic states in molecular systems such as phenanthrene-edge-type hydrocarbons are discussed and compared with those in the monoanions and cations. The complete phase patterns difference between the highest occupied molecular orbitals (HOMO) and the lowest unoccupied molecular orbitals (LUMO) (the atomic orbitals between two neighboring carbon atoms combined in phase (out of phase) in the HOMO are combined out of phase (in phase) in the LUMO) are the main reason that the C-C stretching modes around 1500 cm(-1) afford much larger electron-phonon coupling constants in the excited electronic states than in the charged electronic states. The frequencies of the vibrational modes that play an essential role in the electron-phonon interactions for the excited electronic states are similar to those for the monoanions and cations in phenanthrene-edge-type hydrocarbons. Possible electron pairing and Bose-Einstein condensation in the photoinduced excited electronic states as well as those in the monoanions and cations in molecular systems such as phenanthrene-edge-type hydrocarbons are also discussed.     

Electron-phonon interactions and Jahn-Teller effects in the monocation of corannulene

Electron-phonon interactions in the monocation of corannulene are studied by using the hybrid Hartree-Fock (HF)/density-functional-theory (DFT) method in the Gaussian 98 program package. The C-C stretching mode of 1498 cm(-1) most strongly couples to the e1 highest occupied molecular orbitals (HOMO) in corannulene. The total electron-phonon coupling constant for the monocation (l(HOMO)) of corannulene is estimated to be 0.165 eV. The l(HOMO) value for corannulene is much larger than those for coronene and acenes with similar numbers of carbon atoms. The delocalized electronic structures and the intermediate characteristics between the strong sigma-orbital interactions and weak pi-orbital interactions originating from a bowl-shaped C(5v) geometry are the main reason that the l(HOMO) value for corannulene is much larger than those for planar D(6h) symmetric pi-conjugated coronene and D(2h) symmetric pi-conjugated acenes with similar numbers of carbon atoms. The electron transfer in the positively charged corannulene is also discussed. Intramolecular electron mobility (sigma(intra,monocation)) in the positively charged corannulene is estimated to be smaller than those for the positively charged pi-conjugated acenes and coronene. The reorganization energy for the positively charged corannulene (0.060 eV) is estimated to be larger than those for the positively charged acenes and coronene. The strong orbital interactions between two neighboring carbon atoms in the HOMO of corannulene with the bowl-shaped structure are the main reasons for the calculated results. Thus, the larger overlap integral between two neighboring molecules is needed for the positively charged corannulene to become a better conductor than those for positively charged coronene and acenes. The smaller density of states at the Fermi level n(0) values are enough for the conditions of the attractive electron-electron interactions to be realized in the monocation of corannulene than in the monocations of coronene and acenes with similar numbers of carbon atoms. The multimode problem is also treated in order to investigate how consideration of the multimode problem is closely related to the characteristics of the electron-phonon interactions.     

Novel multifunctional organic semiconductor materials based on 4,8-substituted 1,5-naphthyridine: synthesis, single crystal structures, opto-electrical properties and quantum chemistry calculation

A series of 4,8-substituted 1,5-naphthyridines (1a-1h) have been successfully synthesised by a Suzuki cross-coupling between 4,8-dibromo-1,5-naphthyridine (4) and the corresponding boronic acids (2a-2h) in the presence of catalytic palladium acetate in yields of 41.4-75.8% and have ben well characterized. They are thermally robust with high phase transition temperatures (above 186 °C). Compounds 1b, 1e and 1f crystallized in the monoclinic crystal system with the space groups P2(1)/c, P2(1)/c and P2(1)/n, respectively. All of them show the lowest energy absorption bands (λ(max)(Abs): 294-320 nm), revealing low optical band gaps (2.77-3.79 eV). These materials emit blue fluorescence with λ(max)(Em) ranging from 434-521 nm in dilute solution in dichloromethane and 400-501 nm in the solid state. 4,8-Substituted 1,5-naphthyridines 1a-1h have estimated electron affinities (EA) of (2.38-2.72 eV) suitable for electron-transport materials and ionization potentials (IP) of 4.85-5.04 eV facilitate excellent hole-injecting/hole-transport materials properties. Quantum chemical calculations using DFT B3LYP/6-31G* showed nearly identical the lowest unoccupied molecular orbitals (LUMO) of -2.39 to -2.19 eV and the highest occupied molecular orbitals (HOMO) of -5.33 to -6.84 eV. These results demonstrate the 4,8-substituted 1,5-naphthyridines 1a-1h with a simple architecture might be promising blue-emitting (or blue-green-emitting) materials, electron-transport materials and hole-injecting/hole-transport materials for applications for developing high-efficiency OLEDs.     

Coupled cluster calculations provide a one‐to‐one mapping between calculated and observed transition energies in the electronic absorption spectrum of zinc phthalocyanine

All transitions in the experimentally designated and numbered Q, B, and N bands (< 4.8 eV) of the electronic absorption spectrum of zinc phthalocyanine (ZnPc) are assigned on the basis of one‐to‐one agreement between calculated and experimentally observed transition energies and oscillator strengths. Each band in this range of the spectrum represents a ligand‐based transition that originates from a combination of occupied orbitals and terminates in the lowest unoccupied molecular orbital (LUMO, ). Transition energies in the L and C regions (4.8–6.5 eV) are harder to capture quantitatively, due to the partial Rydberg character of some of the excited states, and so are tentatively assigned here. Most transitions in this range correspond to excitations from the HOMO or lower‐energy orbitals to π orbitals above the LUMO.     

Replacement of 2,2'-bipyridine by 1,4-diazabutadiene acceptor ligands: why the bathochromic shift for [(N empty set N)IrCl(C5Me5)]+ complexes but the hypsochromic shift for (N empty set N)Ir(C5Me5)?

Replacement of 2,2'-bipyridine (bpy) by substituted 1,4-diazabutadiene (R-DAB) alpha-diimine ligands N empty set N leads to a substantial hypsochromic shift of about 0.8 eV for the long-wavelength absorption band in compounds (N empty set N)Ir(C(5)Me(5)) but to a bathochromic absorption shift of about 0.4 eV for the complex ions [(N empty set N)IrCl(C(5)Me(5))](+). DFT calculations on model complexes based on experimental (R-DAB compounds) and geometry-optimized structures (bpy systems) reveal that the low-energy transitions of the cationic chloro complexes are largely of ligand-to-ligand charge-transfer character L'LCT (L = alpha-diimine, L' = Cl) whereas the neutral compounds exhibit pi --> pi transitions between the considerably mixed metal d(pi) and alpha-diimine pi orbitals. The much more pronounced metal-ligand orbital interaction for the R-DAB complexes causes the qualitatively different shifts on replacing the stronger basic bpy by the better pi-acceptors R-DAB. Only the LUMO of the neutral compounds is destabilized on replacement of bpy by R-DAB whereas the LUMO of [(N empty set N)IrCl(C(5)R'(5))](+) and both HOMOs are stabilized through this change.     

Theoretical study of substituent effects on electronic and structural properties of 2,4-diamino-5-para-substituted-phenyl-6-ethyl-pyrimidines

Density functional theory (DFT) method at the level of B3LYP with 6?C311G(d) basis set was used to investigate the effects of a variety of substituents (H, NH₂, NMe₂, OCH₃, CH₃, Cl, Br, CN, NO₂) on the electronic and structural properties of 2,4-diamino-5-p-substituted-phenyl-6-ethyl-pyrimidines. The investigation showed that the atomization energy was affected by substitution. Likewise, the molecular orbitals HOMO and LUMO and energy gap ??E were affected by the substituent. Dipole moment was also affected by the introduction of the substituent. On the other hand, the Mulliken charges at only C1??, C2 and N7, were correlated with both MSP and DSP models.     

Theoretical study of spin-orbit coupling and intersystem crossing in the two-state reaction between Nb(NH2)3 and N2O

The two-state mechanism of the reaction of Nb(NH2)3 with N2O on the singlet and triplet potential energy surfaces has been investigated at the B3LYP level.Crossing points between the potential energy surfaces have been located using different methods.Analysis of the strain model shows that the singlet state of the four-coordinate(N2O)Nb(NH2)3 complex with N2O bonded via terminal N atom coordination(12) is more stable in the initial stage of reaction,since the bending of the N2O fragment [Edef(N2O) = 86.1 kcal mol-1] results in an energy splitting of the doubly degenerate LUMO;the low-energy LUMO can now strongly couple with the occupied Nb-localized d orbitals,forming a back-bond and transferring charge(q = 0.82 e) from Nb(NH2)3 to the N2O ligand.Going from 32 to 12,the reacting system changes spin multiplicity near the MECP(minimal energy crossing point) region,which takes place with a spin crossing barrier of 9.6-10.0 kcal mol-1.Analysis of spin-orbit coupling(SOC) indicates that MECP will produce a significant SOC matrix element.The value of SOC is 111.52 cm-1,due to the electron shift between two perpendicular φ orbitals with the same rotation direction,and the magnitude of the spin-multi-plicity mixing increases in the small energy gap between high-and low-spin states,greatly enhancing the probability of intersystem crossing.The probabilities of single(P1 ISC) and double(P2 ISC) passes estimated at MECP(SOC = 111.52 cm-1) are approximately 1.17×10-2 and 2.32×10-2,respectively.     

The leapfrog principle for boron fullerenes: a theoretical study of structure and stability of B112

Two leapfrog isomers of a B(112) boron fullerene are constructed from small C(28) fullerenes (T(d) and D(2) symmetries) by the leapfrog transformation combined with omnicapping of the new hexagons. Their electronic structure is analyzed using the density functional theory at the B3LYP/SVP and BHLYP/SVP levels. Both isomers are characterized as minima on the potential energy hypersurface with a HOMO-LUMO gap at B3LYP/SVP of 1.7 eV and 1.6 eV (3.1 and 3.0 eV at BHLYP/SVP), respectively. The optimized structure of the helical D(2)-leapfrog is asymmetric, due to radial displacements of the capping atoms. The computed cohesive energies amount to -4.2 eV (～0.04 eV lower than B(80)). The B(112) isomers are isoelectronic to T(d)-C(84) and D(2)-C(84), and HOMO and LUMO orbitals in both isomers closely resemble those of their C(84) homologues. Energetic stability of leapfrog boron fullerenes depends on the isolation of empty hexagon criterion, which is defined by the empty hexagon index based on the total number of empty hexagon pairs and empty hexagon-pentagon fused pairs. The switch of the cap atom to the nearest or farthest empty hexagon destabilizes the cage by 1.6 and 2.7 eV, respectively. The destabilization becomes more enhanced in non-leapfrog structures wherein more caps are displaced.     

Electronic structure and photocatalytic characterization of a novel photocatalyst AgAlO2

A novel photocatalyst, AgAlO2, was prepared by cation exchange reaction and characterized by powder X-ray diffraction. The result showed AgAlO2 crystallizes in the layered orthorhombic structure with space group was Pna2(1). The energy band and electronic structures of AgAlO2 were calculated based on the crystal structure. It was found that AgAlO2 is an indirect band gap semiconductor. The valence band top mainly consists of O-2p orbitals and Ag-4d orbitals and the conduction band bottom is mainly constructed of Ag-5s5p orbitals. The band gap of AgAlO2 was estimated to be about 2.8(1) eV with UV-vis diffuse reflectance spectrometry. The photocatalytic activity of AgAlO2 was characterized by photocatalytically decomposing the dye alizarin red (AR) under visible light irradiation, and AR could be decomposed about 70% under 2 h of visible light irradiation.     

Implications of molecular orbital symmetries and energies for the electron delocalization of inorganic clusters.

Isostructural clusters exhibit contrasting magnetic properties when the number of electrons differs. Surprisingly, the same is true even for isoelectronic cages (e.g. O(h) B6H6(2-) is diatropic, whereas O(h) Si6(2-) is paratropic) or for those with different substitutents (e.g. T(d) B4H4 is paratropic, whereas T(d) B4F4 is diatropic). Indeed, the total nucleus-independent chemical shift (NICS) values, based on shieldings computed at cluster centers, may range considerably in magnitude and even change from diatropic (up-field shifted) to paratropic (down-field shifted). Similarly, individual dissected canonical molecular orbital contributions to the total NICS values computed at the "gauge-including atomic orbitals" (GIAO) level vary greatly. This contrasting behavior arises from molecular orbital energy differences, from the extent of orbital overlap, as well as from symmetry-based selection rules derived from group theory. Differences in magnetic properties may originate from the symmetry of the orbitals; specifically from the forbidden nature of the highest occupied molecular orbital --> lowest unoccupied molecular orbital (HOMO --> LUMO) electronic excitation weighted by the occupied-unoccupied orbital energy difference. Thus, HOMO-NICS values are generally highly paratropic if the HOMO --> LUMO rotational transition is allowed by symmetry selection rules.     

Comparative study of the semiconducting properties of benzothiadiazole and benzobis(thiadiazole) derivatives using computational techniques

Recent literature reports indicate that derivatives of benzothiadiazole (BT) and benzobis(thiadiazole) (BBT), which differs from BT by an extra thiadiazole ring, exhibit good semiconducting properties, such as high electron mobility and low-lying lowest unoccupied molecular-orbital (LUMO) levels. In this study herein, computational techniques like density functional theory (DFT), spin-flip DFT and valence-bond methods are used to analyze the semiconducting properties of these molecules. Calculations at the B3LYP/cc-pVTZ level reveal that all the BBT molecules, including the bare BBT ring, have lower lying LUMO energies (3.70-4.11 eV) compared to the BT derivatives (2.56-3.41 eV) with similar substitution. The reorganization energies (λ(+)/λ(-)) obtained at this level of theory of the BT derivatives are around (225-333)/(246-315) meV, while BBT derivatives have much smaller reorganization energies and these are in the range of (129-259)/(150-230) meV. We observe that the different behavior of BBT is due to the inherited biradicaloid character from the parent molecule tetramethylenebenzene (TMB), a disjoint non-Kekule biradical having non-bonding molecular orbitals (NBMOs) as the highest occupied molecular orbital (HOMO) and LUMO. Additionally, the perturbation of the orbitals of the biradical TMB to obtain BBT is the major cause for the BBT derivatives to have a larger electron affinity (EA) and a smaller HOMO-LUMO gap (HLG) compared to BT derivatives.     

Synthesis of 1-azaspiro[2.4]hepta-1,4,6-trienes and azaspiroconjugation studied by photoelectron spectroscopy

1-Azaspiro[2.4]hepta-1,4,6-trienes 3a-c have been prepared by photolysis or thermolysis of 6-azidofulvenes 5a-c, which were accessible by nucleophilic substitution reactions of the precursors 4a,b or by nucleophilic addition of hydrazoic acid to ethenylidene-cyclopentadiene (6c). The UV photoelectron spectrum of 2-methyl-1-azaspiro[2.4]hepta-1,4,6-triene (3c) has been recorded and analyzed by making use of density functional theory (DFT) B3LYP calculations. Substantial homoconjugative interactions have been determined. The lone-pair orbital n(N) of the 2H-azirine nitrogen atom interacts with the pi 1 orbital of the cyclopentadiene ring. The energies of these orbitals are lowered or increased by 0.95 or 0.91 eV with respect to the two parent compounds cyclopentadiene (7) and 3-methyl-2H-azirine (9), respectively. In addition, in compound 3c the pi (C=N) orbital of the three-membered ring interacts with a sigma orbital of the cyclopentadiene unit and is destabilized by 0.47 eV by this effect.     

Bonding in negative ions: the role of d orbitals in the heavy analogues of pyridine and furan radical anions

We have used a potential wall method to investigate the role of d orbitals in the a(2) singly-occupied molecular orbitals of (2)A(2) negative ion states of two molecular series: pyridine, phosphabenzene, arsabenzene, stibabenzene (C(5)H(5)X, X = {N, P, As, Sb}), and furan, thiophene, selenophene, tellurophene (C(4)H(4)X, X = {O, S, Se, Te}). Unlike for the lower lying doubly occupied orbitals, heteroatom d-carbon p in-phase (bonding) interactions in these a(2) orbitals are clearly identified and explain the 0.5 eV stabilization of the (2)A(2) radical anion state in those compounds where the heteroatoms have d orbitals in the valence shell, compared to compounds where d orbitals are missing in the valence shell of the heteroatoms. The performance of both the potential wall approach and the approximate expression of Tozer and De Proft for calculating negative electron affinities has been also investigated, through a comparison with results obtained using electron-transmission spectroscopy experiments.