Photoelectron spectroscopy of cluster anions of naphthalene and related aromatic hydrocarbons

The electronic structures and structural morphologies of naphthalene cluster anions, (naphthalene)(n)(-) (n=3-150), and its related aromatic cluster anions, (acenaphthene)(n)(-) (n=4-100) and (azulene)(n)(-) (n=1-100), are studied using anion photoelectron spectroscopy. For (naphthalene)(n) (-) clusters, two isomers coexist over a wide size range: isomers I and II-1 (28 < or = n < or =60) or isomers I and II-2 (n > or = ~60). Their contributions to the photoelectron spectra can be separated using an anion beam hole-burning technique. In contrast, such an isomer coexistence is not observed for (acenaphthene)(n) (-) and (azulene)(n) (-) clusters, where isomer I is exclusively formed throughout the whole size range. The vertical detachment energies (VDEs) of isomer I (7 < or = n < or = 100) in all the anionic clusters depend linearly on n(-13) and their size-dependent energetics are quite similar to one another. On the other hand, the VDEs of isomers II-1 and II-2 produced in (naphthalene)(n)(-) clusters with n > or = approximately 30 remain constant at 0.84 and 0.99 eV, respectively, 0.4-0.6 eV lower than those of isomer I. Based upon the ion source condition dependence and the hole-burning photoelectron spectra experiments for each isomer, the energetics and characteristics of isomers I, II-1, and II-2 are discussed: isomer I is an internalized anion state accompanied by a large change in its cluster geometry after electron attachment, while isomers II-1 and II-2 are crystal-like states with little structural relaxation. The nonappearance of isomers II-1 and II-2 for (acenaphthene)(n)(-) and (azulene)(n)(-) and a comparison with other aromatic cluster anions indicate that a highly anisotropic and symmetric pi-conjugated molecular framework, such as found in the linear oligoacenes, is an essential factor for the formation of the crystal-like ordered forms (isomers II-1 and II-2). On the other hand, lowering the molecular symmetry makes their production unfavorable.     

Mass spectrometry and photoelectron spectroscopy of tetracene cluster anions, (tetracene)n- (n = 1-100): evidence for the highly localized nature of polarization in a cluster analogue of oligoacene crystals

Photoelectron spectroscopy of tetracene cluster anions, (tetracene)n- (n = 1-100), reveals the coexistence of two types of isomers, designated as isomers I and II-1 (n = 10-50) or isomers I and II-2 (n > 60), in a wide size range. The vertical detachment energies (VDEs) of isomer I increase persistently due to polarization and structural relaxation effects, where a monomeric anion core is encompassed with geometrically reorganized neutral molecules. Conversely, a characteristic ion distribution in the mass spectrum of (tetracene)n-ensues from the two-dimensional (2D) herringbone-type ordering of isomer II-1, whose VDEs remain constant at 1.80 eV for n >/= 14. Also, isomer II-2, presumably adopting multilayered structural motifs, exhibits invariable VDEs of 2.0 eV, a manifestation of significant charge screening effects in these isomers. The invariable nature of the VDEs of isomers II-1 and II-2 unambiguously demonstrates a largely localized nature of polarization induced by the excess charge residing in microscopic crystal-like environments. Surprisingly, only 14 tetracene molecules within a 2D herringbone-type layer including an excess charge can provide the charge stabilization energy corresponding to approximately 80% of that of the crystal, and the rest of the energy is provided by polarization of neutral molecules in adjacent layers.     

Mass spectrometry and photoelectron spectroscopy of o-, m-, and p-terphenyl cluster anions: the effect of molecular shape on molecular assembly and ion core character

Mass spectrometry and photoelectron spectroscopy of o-, m-, and p-terphenyl cluster anions, (o-TP)n(-) (n = 2-100), (m-TP)n(-) (n = 2-100), and (p-TP)n(-) (n = 1-100), respectively, are conducted to investigate the effect of molecular shape on the molecular aggregation form and the resultant ion core character of the clusters. For (o-TP)n(-) and (m-TP)n(-), neither magic numbers nor discernible isomers are observed throughout the size range. Furthermore, their vertical detachment energies (VDEs) increase up to large n and depend linearly on n(-1/3), implying that they possess a three-dimensional (3D), highly reorganized structure encompassing a monomeric anion core. For (p-TP)n(-), in contrast, prominent magic numbers of n = 5, 7, 10, 12, and 14 are observed, and the VDEs show pronounced irregular shifts below n = 10, while they remain constant above n = 14 (isomer A). These results can be rationalized with two-dimensional (2D) orderings of p-TP molecules and different types of 2D shell closure at n = 7 and 14, the monomeric and multimeric anion core, respectively. Above n = 16, the new feature (isomer B) starts to appear at the higher binding side of isomer A, and it becomes dominant with n, while isomer A gradually disappears for larger sizes. In contrast to isomer A, the VDEs of isomer B continuously increase with the cluster size. This characteristic size evolution suggests that the transition to modified 2D aggregation forms from 2D ones occurs at around n = 20.     

Theoretical characterization of four distinct isomer types in hydrated-electron clusters, and proposed assignments for photoelectron spectra of water cluster anions

Water cluster anions, (H(2)O)(N)(-), are examined using mixed quantum/classical molecular dynamics based on a one-electron pseudopotential model that incorporates many-body polarization and predicts vertical electron detachment energies (VDEs) with an accuracy of ~0.1 eV. By varying the initial conditions under which the clusters are formed, we are able to identify four distinct isomer types that exhibit different size-dependent VDEs. On the basis of a strong correlation between the electron's radius of gyration and its optical absorption maximum, and extrapolating to the bulk limit (N → ∞), our analysis supports the assignment of the "isomer Ib" data series, observed in photoelectron spectra of very cold clusters, as arising from cavity-bound (H(2)O)(N)(-) cluster isomers. The "isomer I" data reported in warmer experiments are assigned to surface-bound isomers in smaller clusters, transitioning to partially embedded isomers in larger clusters. The partially embedded isomers are characterized by a partially formed solvent cavity at the cluster surface, and they are spectroscopically quite similar to internalized cavity isomers. These assignments are consistent with various experimental data, and our theoretical characterization of these isomers sheds new light on a long-standing assignment problem.     

Electronic relaxation dynamics of water cluster anions

The electronic relaxation dynamics of water cluster anions, (H(2)O)(n)(-), have been studied with time-resolved photoelectron imaging. In this investigation, the excess electron was excited through the p<--s transition with an ultrafast laser pulse, with subsequent electronic evolution monitored by photodetachment. All excited-state lifetimes exhibit a significant isotope effect (tau(D)2(O)/tau(H)2(O) approximately 2). Additionally, marked dynamical differences are found for two classes of water cluster anions, isomers I and II, previously assigned as clusters with internally solvated and surface-bound electrons, respectively. Isomer I clusters with n > or = 25 decay exclusively by internal conversion, with relaxation times that extrapolate linearly with 1/n toward an internal conversion lifetime of 50 fs in bulk water. Smaller isomer I clusters (13 < or = n < or = 25) decay through a combination of excited-state autodetachment and internal conversion. The relaxation of isomer II clusters shows no significant size dependence over the range of n = 60-100, with autodetachment an important decay channel following excitation of these clusters. Photoelectron angular distributions (PADs) were measured for isomer I and isomer II clusters. The large differences in dynamical trends, relaxation mechanisms, and PADs between large isomer I and isomer II clusters are consistent with their assignment to very different electron binding motifs.     

Site-specific addition of D(2)O to the (H(2)O)(6)(-) "hydrated electron" cluster: isomer interconversion and substitution at the double H-bond acceptor (AA) electron-binding site

We report the results of an experimental study designed to establish whether, once formed, one of the isomer classes of the hydrated electron clusters, (H(2)O)(n)(-), can interconvert with others when a water molecule is added by condensation. This is accomplished in an Ar-cluster mediated approach where a single intact D(2)O molecule is collisionally incorporated into argon-solvated water hexamer anions, creating the isotopically labeled D(2)O.(H(2)O)(6)(-).Ar(n) heptamer anion. Photoelectron and infrared predissociation spectroscopies are employed both to characterize the isomers generated in the condensation event and to track the position that the D(2)O label adopts within these isomeric structures. Despite the fact that the water hexamer anion precursor clusters initially exist in the isomer I form, incorporation of D(2)O produces mostly isomers I' and II in the labeled heptamer, which bind the electron more (I') or less (II) strongly than does the isomer I class. Isomers I and I' are known to feature electron binding primarily onto a single water molecule that resides in an AA (A = H-bond acceptor) site in the network. Surprisingly, the D(2)O molecule can displace this special electron-binding H(2)O molecule such that the anionic cluster retains the high binding arrangement. In the more weakly binding isomer II clusters, the D(2)O molecule fractionates preferentially to sites that give rise to the vibrational signature of isomer II.     

Photoelectron spectroscopic study of the hydrated nucleoside anions: Uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1)

The hydrated nucleoside anions, uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1), have been prepared in beams and studied by anion photoelectron spectroscopy in order to investigate the effects of a microhydrated environment on parent nucleoside anions. Vertical detachment energies (VDEs) were measured for all eight anions, and from these, estimates were made for five sequential anion hydration energies. Excellent agreement was found between our measured VDE value for thymidine(-)(H(2)O)(1) and its calculated value in the companion article by S. Kim and H. F. Schaefer III.     

Solvation-induced cluster anion core switching from NNO2(-)(N2O)n-1 to O(-)(N2O)n

We report a photoelectron imaging study of the [O(N(2)O)(n)](-), 0or=4 (and up to at least n=9) signatures of an O(-) core are predominantly observed. Photofragmentation studies at 355 nm support these results.     

Exploring the rich energy landscape of sulfate-water clusters SO4(2-) (H2O)(n=3-7): an electronic structure approach

We present a reinvestigation of sulfate-water clusters SO4(2-) (H2O)(n=3-7), which involves several new aspects. Using a joint molecular mechanics/first principles approach, we perform exhaustive searches for stable cluster geometries, showing that the sulfate-water landscape is much richer than anticipated previously. We check the compatibility of the new structures with experiment by comparing vertical detachment energies (VDEs) calculated at the B3LYP/6-311++G** level of theory and determine the energetic ordering of the isomers at the RI-MP2/aug-cc-pVTZ level. Our results are bench-marked carefully against reference energies of estimated CCSD(T)/aug-cc-VTZ quality and VDEs of CCSD(T)/aug-cc-pVDZ quality. Furthermore, we calculate anharmonic vibrational corrections for up to the n = 6 clusters, which are shown to be significant for isomer energy ordering. We use energy decomposition analysis (EDA) based on the absolutely localized fragment (ALMO) expansion to gain chemical insight into the binding motifs.     

Probing isomer interconversion in anionic water clusters using an Ar-mediated pump-probe approach: Combining vibrational predissociation and velocity-map photoelectron imaging spectroscopies

We present the first results from an experiment designed to explore barriers for interconversion between isomers of cluster anions using an Ar-cluster mediated pump-probe technique. In this approach, anions are generated with many Ar atoms attached, and one of the isomers present is selectively excited by tuning an infrared laser to one of the isomer's characteristic vibrational resonances. The excited cluster is then cooled by evaporation of Ar atoms, and the isomer distribution in the lighter daughter ions is measured after secondary mass selection by recording their photoelectron spectra using velocity-map imaging. We apply the method to the water hexamer anion, (H(2)O)(6) (-), which is known to occur in two isomeric forms with different electron-binding energies. We find that conversion of the high-binding (type I) form to the low-binding (type II) isomer is not efficiently driven in (H(2)O)(6) (-) with excitation energies in the 0.4 eV range even though it is possible to create both isomers in abundance in the ion source. This observation is discussed in the context of the competition between isomerization and electron autodetachment, which depends on the relative positions of the neutral and ionic potential surfaces along the isomerization pathway. Application of the method to the more complex heptamer ion, however, does reveal that interconversion is available among the highest binding isomer classes (I and I(')).     

Probing the structural and magnetic properties of transition metal-benzene anion complexes

Two types of transition metal-benzene anion complexes, (titanium)(n)(benzene)(m)? and (cobalt)(n)(benzene)(m)? (n ≤ 2, m ≤ 3) have been determined using density functional theory. The photoelectron spectra of Ti(n)Bz(m)? and Co(n)Bz(m)? (n ≤ 2, m ≤ 3) were discussed from the perspective of quantum chemical calculations of the vertical detachment energies (VDEs) of several low-energy isomers obtained by the structural optimization procedure. The binding of Ti and Co atoms to benzene molecules is accounted by 3d-π bonds, as revealed by the molecular orbitals. The topology of the electronic density has been analyzed, suggesting that the C-C bonds were weakened in the transition metal-benzene complexes in comparison to those in free benzene. Spin density distribution results show the spin densities for Ti(n)Bz(m)? and Co(n)Bz(m)? (n ≤ 2, m ≤ 3) reside mainly on the metal Ti and Co centers (70%-90%). A shift to lower magnetic moment with respect to the pure titanium/cobalt cluster anions indicates the solvent benzene molecule acts to demagnetize the bare titanium/cobalt cluster anions.     

Photoelectron imaging and theoretical calculations of gold-silver hydrides: comparing the characteristics of Au, Ag and H in small clusters

Structures and electronic properties of the mixed metal hydride anions AuAgH(-), Au(2)AgH(-), AuAg(2)H(-) and their neutrals are studied using anionic photoelectron imaging and theoretical calculations. The three isomers of AuAgH(-) are determined to be linear and those of AuAgH are determined to have C(s) symmetry. The structures of Au(2)AgH(-), AuAg(2)H(-) and their corresponding neutrals are determined to be planar with C(s) or C(2v) symmetries. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) of these anions are reported. Similar to the homonuclear Au(m)(-) and Ag(n)(-) clusters, the metal hydride anions with an even number of valence electrons have higher VDEs than those with an odd number. Variation of the VDEs of these metal hydride anions with interchange of Au, Ag and H (for example Au(m)Ag(n)(-)→ Au(m-1)Ag(n+ 1)(-), or Au(m-1)Ag(n)H(-)) will be shown to be characterized by the electronegativities of Au, Ag and H. The results presented in this study provide important insights into the similar and different characteristics of these three elements in small clusters.     

Photoelectron spectroscopy of the [glycine x (H2O)(1,2)]- clusters: sequential hydration shifts and observation of isomers

The electron binding energies of the small hydrated amino acid anions, [glycine x (H2O)(1,2)]-, are determined using photoelectron spectroscopy. The vertical electron detachment energies (VDEs) are found to increase by approximately 0.12 eV with each additional water molecule such that the higher electron binding isomer of the dihydrate is rather robust, with a VDE value of 0.33 eV. A weak binding isomer of the dihydrate is also recovered, however, with a VDE value (0.14 eV) lower than that of the monohydrate. Unlike the situation in the smaller (n < or = 13) water cluster anions, the [Gly x (H2O)(n > or = 6)]- clusters are observed to photodissociate via water monomer evaporation upon photoexcitation in the O-H stretching region. We discuss this observation in the context of the mechanism responsible for the previously observed [S. Xu, M. Nilles, and K. H. Bowen, Jr., J. Chem. Phys. 119, 10696 (2003)] sudden onset in the cluster formation at [Gly x (H2O)5]-.     

Size-dependent metamorphosis of electron binding motif in cluster anions of primary amide molecules

Electron binding motifs in cluster anions of primary amides, (acetamide)(n)(-) and (propionamide)(n)(-), were studied with photoelectron spectroscopy. For both the amides, two band series due to distinct isomeric species in the multipole-bound states were found in the low electron binding energy region (<~0.4 eV) of the photoelectron spectra at the excitation wavelength of 1064 nm. In the case of acetamide, the isomer of higher band peak energies is predominant for 6≤ n ≤ 8, but it vanishes completely for n ≥ 9 to be replaced with the lower energy isomer. The same spectral behavior was seen for propionamide exhibiting an exception at n = 7. The isomers appearing in the lower and higher energy sides were attributed to the straight and folded forms of ladder-like hydrogen bond network structures, respectively, on the basis of density functional calculations. In the folded forms, the excess electron is held in the space between two terminal amide molecules of the ladder-like networks. Referring to calculations of potential energy curves with respect to the folding coordinate of the ladder-like networks, it is inferred that the major isomer alternation between n = 8 and 9 originates from an increase of stiffness of the molecular ladders depending on the cluster sizes. In photoelectron spectra at the 355 nm excitation, the valence anion state having a band peak around 2.5 eV was observed to emerge with threshold sizes of n = 13 and 9 for acetamide and propionamide, respectively. Static and dynamical effects of alkyl groups on the electron binding motifs are discussed in comparison with the previous study on formamide cluster anions.     

Photoelectron imaging of tetrahydrofuran cluster anions (THF)(n) (-) (1≤n≤100)

Anionic tetrahydrofuran clusters (THF)(n) (-) (1≤n≤100) are studied with photoelectron imaging as gas-phase precursors for electrons solvated in THF. Photoelectron spectra of clusters up to n=5 show two peaks, one of which is attributed to a solvated open chain radical anion and the other to the closed THF ring. At n=6, the spectra change shape abruptly, which become more characteristic of (THF)(n) (-) clusters containing solvated electrons. From n=6-100, the vertical detachment energies (VDEs) of these solvated electron clusters increase from 1.96 to 2.71 eV, scaling linearly with n(-1/3). For fully deuterated (THF-d8)(n) (-) clusters, the apparent transition to a solvated electron cluster is delayed to n=11. Extrapolation of the VDEs to infinite cluster size yields a value of 3.10 eV for the bulk photoelectric threshold. The relatively large VDEs at onset and small stabilization with increasing cluster size compared to other solvated electron clusters may reflect the tendency of the bulk solvent to form preexisting voids that can readily solvate a free electron.     

Vanadogermanate cluster anions

Three novel vanadogermanate cluster anions have been synthesized by hydrothermal reactions. The cluster anions are derived from the (V(18)O(42)) Keggin cluster shell by substitution of V=O(2+) "caps" by Ge(2)O(OH)(2)(4+) species. In Cs(8)[Ge(4)V(16)O(42)(OH)(4)].4.7H(2)O, 1, (monoclinic, space group C2/c (No. 15), Z = 8, a = 44.513(2) A, b = 12.7632(7) A, c = 22.923(1) A, beta = 101.376(1) degrees ) and (pipH(2))(4)(pipH)(4)[Ge(8)V(14)O(50).(H(2)O)] (pip = C(4)N(2)H(10)), 2 (tetragonal, space group P4(2)/nnm (No. 134), Z = 2, a = 14.9950(7) A, c = 18.408(1) A), two and four VO(2+) caps are replaced, respectively, and each cluster anion encapsulates a water molecule. In K(5)H(8)Ge(8)V(12)SO(52).10H(2)O, 3, (tetragonal, space group I4/m (No. 87), Z = 2, a = 15.573(1) A, c = 10.963(1) A), four VO(2+) caps are replaced by Ge(2)O(OH)(2)(4+) species, and an additional two are omitted. The cluster ion in 3 contains a sulfate anion disordered over two positions. The cluster anions are analogous to the vanadoarsenate anions [V(18)(-)(n)()As(2)(n)()O(42)(X)](m)(-) (X = SO(3), SO(4), Cl; n = 3, 4) previously reported.     

Ar(n)HF van der Waals clusters revisited: II. Energetics and HF vibrational frequency shifts from diffusion Monte Carlo calculations on additive and nonadditive potential-energy surfaces for n=1-12

The ground-state energies and HF vibrational frequency shifts of Ar(n)HF clusters have been calculated on the nonadditive potential-energy surfaces (PESs) for n=2-7 and on the pairwise-additive PESs for the clusters with n=1-12, using the diffusion Monte Carlo (DMC) method. For n>3, the calculations have been performed for the lowest-energy isomer and several higher-lying isomers which are the closest in energy. They provide information about the isomer dependence of the HF redshift, and enable direct comparison with the experimental data recently obtained in helium nanodroplets. The agreement between theory and experiment is excellent, in particular, for the nonadditive DMC redshifts. The relative, incremental redshifts are reproduced accurately even at the lower level of theory, i.e., the DMC and quantum five-dimensional (rigid Ar(n)) calculations on the pairwise-additive PESs. The nonadditive interactions make a significant contribution to the frequency shift, on the order of 10%-12%, and have to be included in the PESs in order for the theory to yield accurate magnitude of the HF redshift. The energy gaps between the DMC ground states of the cluster isomers are very different from the energy separation of their respective minima on the PES, due to the considerable variations in the intermolecular zero-point energy of different Ar(n)HF isomers.     

Unraveling the mechanisms of O2 activation by size-selected gold clusters: transition from superoxo to peroxo chemisorption

The activation of dioxygen is a key step in CO oxidation catalyzed by gold nanoparticles. It is known that small gold cluster anions with even-numbered atoms can molecularly chemisorb O(2) via one-electron transfer from Au(n)(-) to O(2), whereas clusters with odd-numbered atoms are inert toward O(2). Here we report spectroscopic evidence of two modes of O(2) activation by the small even-sized Au(n)(-) clusters: superoxo and peroxo chemisorption. Photoelectron spectroscopy of O(2)Au(8)(-) revealed two distinct isomers, which can be converted from one to the other depending on the reaction time. Ab initio calculations show that there are two close-lying molecular O(2)-chemisorbed isomers for O(2)Au(8)(-): the lower energy isomer involves a peroxo-type binding of O(2) onto Au(8)(-), while the superoxo chemisorption is a slightly higher energy isomer. The computed detachment transitions of the superoxo and peroxo species are in good agreement with the experimental observation. The current work shows that there is a superoxo to peroxo chemisorption transition of O(2) on gold clusters at Au(8)(-): O(2)Au(n)(-) (n = 2, 4, 6) involves superoxo binding and n = 10, 12, 14, 18 involves peroxo binding, whereas the superoxo binding re-emerges at n = 20 due to the high symmetry tetrahedral structure of Au(20), which has a very low electron affinity. Hence, the two-dimensional (2D) Au(8)(-) is the smallest anionic gold nanoparticle that prefers peroxo binding with O(2). At Au(12)(-), although both 2D and 3D isomers coexist in the cluster beam, the 3D isomer prefers the peroxo binding with O(2).     

Ab initio molecular-orbital study of structures and energetics of Si3H3 neutral and anion

The geometric structures and isomeric stabilities of various stationary points in Si(3)H(3) neutral and its anion are investigated at the coupled-cluster singles, doubles (triples) [CCSD(T)] level of theory. For geometrical surveys, the basis sets used are of the Dunning's correlation consistent basis sets of triple-zeta quality for the neutral. To the anions, the Dunning's correlation consistent basis sets of double-zeta quality with diffuse functions are applied. For the three lower-lying anion isomers, the Dunning's correlation consistent basis sets of triple-zeta quality with diffuse functions (aug-cc-pVTZ) are also used. The final energies for the optimized stationary points are calculated at the CCSD(T) level of theory with the aug-cc-pVTZ basis sets. The basis sets of 6-311++G(3df,2pd) were also used for the lower-lying anion isomers. The Gaussian-2 method was performed only for the lower-lying anion isomers to clarify the relative stabilities. The global minimum neutral 1 (C(1):(2)A) has an unsymmetrical hydrogen-bridged bond; the conformer 2 in C(s) symmetry is a saddle point connecting the two equivalent isomers 1. Two lower-lying isomers (3 and 4) are also predicted within the energy range of 20 kJmol. In the anion, however, the conformer 4 (C(s):(1)A(')) with five formal valence electrons is a global minimum. Two more isomers (2 and 3) lie within 20 kJmol as in the neutral; the conformer 1 converts to the isomer 2. The quartets for the neutrals and diradical triplets for the anions were further studied; lower-lying quartets and triplets, competing with the corresponding doublet and singlet, respectively, were not found in the present systems. The vertical and adiabatic electron affinities of the global minimum neutral 1, producing the second lowest-lying anion isomer 2, amount to 2.18 and 2.35 eV, respectively, at the CCSD(T)/aug-cc-pVTZ level of theory. The electron addition to the third lowest-lying neutral isomer 4 produces the largest vertical electron affinities of 2.48 eV. The D(3h) structure, being the global minimum in the corresponding Si(3)H(3) (+) cation (trisilacyclopropenyl cation), converts to the isomer 8 (C(s)) or 11 (C(2)) due to the Jahn-Teller effect in the Si(3)H(3) neutral.     

Characterization of solvated electrons in hydrogen cyanide clusters: (HCN)n- (n=3, 4)

Theoretical studies of the solvated electrons (HCN)n- (n=3, 4) reveal a variety of electron trapping possibilities in the (HCN)n (n=3, 4) clusters. Two isomers for (HCN)3- and four isomers for (HCN)4- are obtained at the MP2aug-cc-pVDZ+dBF (diffusive bond functions) level of theory. In view of vertical electron detachment energies (VDEs) at the CCSD(T) level, the excess electron always "prefers" locating in the center of the system, i.e., the isomer with higher coordination number shows larger VDE value. However, the most stable isomers of the solvated electron state (HCN)3- and (HCN)4- are found to be the linear Cinfinitynu and Dinfinityh structures, respectively, but not the fullyl symmetric structures which have the largest VDE values.