Cycloaddition reactions of 16-electron d4 metallocene complexes with C60: a theoretical study

The potential-energy surfaces of the cycloaddition reaction Cp(2)M+C60-->Cp(2)M(C60) (Cp=eta5-C(5)H(5); M=Cr, Mo, and W) were studied at the B3LYP/LANL2DZ level of theory. Two competing reaction pathways were found, which can be classified as [6,5] attack (path A) and [6,6] attack (path B). Given the same reaction conditions, the [6,6]-attack pathway for cycloaddition to C60 is more favorable than the [6,5]-attack pathway, both kinetically and thermodynamically. A qualitative model, based on the theory of Pross and Shaik, was used to develop an explanation for the reaction barrier heights. Thus, our theoretical findings suggest that the singlet-triplet splitting DeltaE(st) (=E(triplet)-E(singlet)) of the 16-electron d4 Cp(2)M and C60 species are a guide to predicting their reactivity towards cycloaddition. Our model results demonstrate that the propensity for cycloaddition to C60 increases in the order Cp(2)Cr相似文献   

Origin of rotational barriers of the N-N bond in hydrazine: NBO analysis

Hydrazine passes through two transition states, TS1 (phi = 0 degrees ) and TS2 (phi = 180 degrees ), in the course of internal rotation around its N-N bond. The origin of the corresponding rotational barriers in hydrazine has been extensively studied by experimental and theoretical methods. Here, we used natural bond orbital (NBO) analysis and energy decomposition of rotational barrier energy (DeltaE(barrier)) to understand the origin of the torsional potential energy profile of this molecule. DeltaE(barrier) was dissected into structural (DeltaE(struc)), steric exchange (DeltaE(steric)), and hyperconjugative (DeltaE(deloc)) energy contributions. In both transition states, the major barrier-forming contribution is DeltaE(deloc). The TS2 barrier is lowered by pyramidalization of nitrogen atoms through lowering DeltaE(struc), not by N-N bond lengthening through lowering DeltaE(steric). Higher pyramidality of nitrogen atoms of TS2 than that of TS1 explains well why the N-N bond of TS2 is longer than that of TS1. Finally, the steric repulsion between nitrogen lone pairs does not determine the rotational barrier; nuclear-nuclear Coulombic repulsion between outer H/H atoms in TS1 plays an important role in increasing DeltaE(struc). Taken together, we explain the reason for the different TS1 and TS2 barriers. We show that NBO analysis is a useful tool for understanding structures and potential energy surfaces of compounds containing the N-N bond.     

Vibronic states in single molecules: C60 and C70 on ultrathin Al2O3 films

Vibronic states are observed in single C(60) and C(70) molecules by scanning tunneling microscopy. When single fullerene molecules are adsorbed on a thin layer of Al(2)O(3) grown on a NiAl(110) substrate, equally spaced features are observed in the differential conductance (dI/dV), which are clearly resolved in d(2)I/dV(2) spectra. These features are attributed to the vibronic states of the molecule. The vibronic progressions are sensitive to the molecular orientations and can have different spacings in different electronic bands of the same molecule. For C(60,) these vibronic states are associated with the intramolecular A(g) and H(g) vibrational modes. Vibronic states are not resolved in molecules adsorbed on the metal surface. However, inelastic electron tunneling spectroscopy exhibits a vibrational mode at 64 meV for C(60) and 61 meV for C(70) adsorbed on NiAl(110).     

Mechanisms of the rotational dynamics of C70 in C70-cubane heteromolecular crystals

Fullerenes and cubane (C(8)H(8)) can be arranged to form heteromolecular crystals that exhibit interesting crystal phases. Experimental measurements indicate a rotor-stator phase for C(60)-cubane crystals in which the C(60) molecules rotate freely whereas cubane molecules are essentially static. A similar phase is found for C(70)-cubane crystals but, due to C(70)'s asymmetry, hindered rotations can be observed in specific crystal phases. Details of the rotational dynamics of the fullerenes in these heteromolecular crystals are difficult to be completely assessed by experiments. To this end, we have performed classical molecular dynamics simulations of C(70)-cubane crystals to investigate the behavior of C(70) fullerenes and cubanes in the face-centered cubic and body-centered tetragonal crystallographic phases. Our simulations show that, in the cubic phase, C(70) molecules are allowed to freely rotate whereas cubanes act as molecular bearings. In the tetragonal phase, the cubane molecules also remain practically fixed and the rotation of C(70) fullerenes becomes hindered. In this phase, C(70) molecules rotate around the fivefold axis, which in turn precesses about the c crystallographic direction of the unit cell. Details regarding the dynamics (e.g., energy barriers, reorientational relaxation processes, and phonon-libration coupling) of the C(70) molecules in both crystal phases are discussed. In general, our results agree with previous experimental findings for C(70)-cubane crystals.     

Infrared-vacuum ultraviolet pulsed field ionization-photoelectron study of C2H4(+) using a high-resolution infrared laser

The infrared (IR)-vacuum ultraviolet (VUV)-pulsed field ionization-photoelectron (IR-VUV-PFI-PE) spectrum for C2H4(X1A(g), v11 = 1, N'(Ka'Kc') = 3(03)) in the VUV range of 83,000-84,800 cm(-1) obtained using a single mode infrared laser revealed 24 rotationally resolved vibrational bands for the ion C2H4(+)(X2B(3u)) ground state. The frequencies and symmetry of the vibrational bands thus determined, together with the anharmonic frequency predictions calculated at the CCSD(T)/aug-cc-pVQZ level, have allowed the unambiguous assignment of these vibrational bands. These bands are mostly combination bands. The measured frequencies of these bands yield the fundamental frequencies for v8+ = 1103 +/- 10 cm(-1) and v10+ = 813 +/- 10 cm(-1) of C2H4(+)(X2B(3u)), which have not been determined previously. The present IR-VUV-PFI-PE study also provides truly rovibrationally selected and resolved state-to-state cross sections for the photoionization transitions C2H4(X1A(g); v11, N'(Ka'Kc')) --> C2H4(+)(X2B(3u); vi+, N+(Ka+Kc+)), where N'(Ka'Kc') denotes the rotational level of C2H4(X1A(g); v11), and vi+ and N+(Ka+Kc+) represent the vibrational and rotational states of the cation.     

Ab initio chemical kinetic study on the reactions of ClO with C2H2 and C2H4

The mechanisms for the reactions of ClO with C(2)H(2) and C(2)H(4) have been investigated at the CCSD(T)/CBS level of theory. The results show that in both systems, the interaction between the Cl atom of the ClO radical and the triple and double bonds of C(2)H(2) and C(2)H(4) forms prereaction van der Waals complexes with the O-Cl bond pointing perpendicularly toward the π-bonds, both with 2.1 kcal/mol binding energies. The mechanism is similar to those of the HO-C(2)H(2)/C(2)H(4) systems. The rate constants for the low energy channels have been predicted by statistical theory. For the reaction of ClO and C(2)H(2), the main channels are the production of CH(2)CO + Cl (k(1a)) and CHCO + HCl (k(1b)), with k(1a) = 1.19 × 10(-15)T(1.18) exp(-5814/T) and k(1b) = 6.94 × 10(-21) × T(2.60) exp(-6587/T) cm(3) molecule(-1) s(-1). For the ClO + C(2)H(4) reaction, the main pathway leads to C(2)H(4)O + Cl (k(2a)) with the predicted rate constant k(2a) = 2.13 × 10(-17)T(1.52) exp(-3849/T) in the temperature range of 300-3000 K. These rate constants are pressure-independent below 100 atm.     

Thermodynamic properties of the C5, C6, and C8 n-alkanes from ab initio electronic structure theory

The heats of formation for the n-alkanes C(n)H(n+2) for n = 5, 6, and 8 have been calculated using ab initio molecular orbital theory. Coupled-cluster calculations with perturbative triples (CCSD(T)) were employed for the total valence electronic energies. Correlation-consistent basis sets were used, up through the augmented quadruple zeta, to extrapolate to the complete basis set limit. Geometries were optimized at the B3LYP/TZVP and MP2/aug-cc-pVTZ levels. The MP2 geometries were used in the CCSD(T) calculations. Frequencies were determined at the density functional level (B3LYP/TZVP), and scaled zero point energies were calculated from the B3LYP frequencies. Core/valence, scalar relativistic, and spin-orbit corrections were included in an additive fashion to predict the atomization energies. The core/valence corrections are not small, (approximately 1.1 kcal/mol per carbon unit) and cannot be neglected for chemical accuracy. The calculated deltaH(298)f values are -35.0, -40.2, and -50.2 kcal/mol for C5H12, C6H14, and C8H18, respectively, in excellent agreement with the respective experimental values of -35.11 +/- 0.19, -39.89 +/- 0.19, and -49.90 +/- 0.31 kcal/mol. Isodesmic reaction energies are presented for some simple reactions involving C8H18 and are shown not to be strongly method dependent.     

A computational study of cycloaddition reactions of d8 metal tetroxide (iron, ruthenium, osmium) complexes with C60

The potential energy surfaces of the cycloaddition reactions MO(4)(NC(5)H(5))(2) + C(60)→ MO(4)(NC(5)H(5))(2)(C(60)) (M = Fe, Ru, and Os) have been studied at the B3LYP/LANL2DZ level of theory. It has been found that there should be two competing pathways in these reactions, which can be classified as a [6,5]-attack (path A) and a [6,6]-attack (path B). Our theoretical calculations indicate that, given the same reaction conditions, the cycloaddition reaction of C(60)via [6,6]-attack is more favorable than that via [6,5]-attack both kinetically and thermodynamically. This is in good agreement with the available experimental observations. A qualitative model, which is based on the theory of Pross and Shaik, has been used to develop an explanation for the barrier heights. As a result, our theoretical findings suggest that the singlet-triplet splitting ΔE(st) (= E(triplet)- E(singlet)) of the d(8) MO(4)(NC(5)H(5))(2) and C(60) species can be a guide to predict their reactivity towards cycloaddition. Our model results demonstrate that the reactivity of d(8) metal tetroxide cycloaddition to C(60) decreases in the order FeO(4)(NC(5)H(5))(2) > RuO(4)(NC(5)H(5))(2) > OsO(4)(NC(5)H(5))(2). In consequence, we show that both electronic and geometric effects play a decisive role in determining the energy barriers as well as the reaction enthalpy.     

Theoretical studies on the role of pi-electron delocalization in determining the conformation of N-benzylideneaniline with three types of LMO basis sets

To understand the role of pi-electron delocalization in determining the conformation of the NBA (Ph-N==CH-Ph) molecule, the following three LMO (localized molecular orbital) basis sets are constructed: a LFMO (highly localized fragment molecular orbital), an NBO (natural bond orbital), and a special NBO (NBO-II) basis sets, and their localization degrees are evaluated with our suggesting index D(L). Afterward, the vertical resonance energy DeltaE(V) is obtained from the Morokuma's energy partition over each of three LMO basis sets. DeltaE(V) = DeltaE(H) (one electron energy) + DeltaE(two) (two electron energy), and DeltaE(two) = DeltaE(Cou) (Coulomb) + DeltaE(ex) (exchange) + DeltaE(ec) (or SigmaDeltaE(n)) (electron correction). DeltaE(H) is always stabilizing, and DeltaE(Cou) is destabilizing for all time. In the case of the LFMO basis set, DeltaE(Cou) is so great that DeltaE(two) > |DeltaE(H)|. Therefore, DeltaE(V) is always destabilizing, and is least destabilizing at about the theta = 90 degrees geometry. Of the three calculation methods such as HF, DFT, and MPn (n = 2, 3, and 4), the MPn method provides DeltaE(V) with the greatest value. In the case of the NBO basis set, on the contrary, DeltaE(V) is stabilizing due to DeltaE(Cou) being less destabilizing, and it is most stabilizing at a planar geometry. The LFMO basis set has the highest localization degree, and it is most appropriate for the energy partition. In the NBA molecule, pi-electron delocalization is destabilization, and it has a tendency to distort the NBA molecular away from its planar geometry as far as possible.     

He+C60↔(He@C60)的反应势垒研究

The reaction barriers of (He+C60(He＠60)) have been calculated by the quantum-chemical method EHMO/ASED in the following four paths: (1) penetrate through the pentagon on the C60 cage; (2) penetrate through the hexagon on the C60 cage,(3) penetrate through the short bond; (4) penetrate through the long bond. Corresponding to each path, there are two choices: (a) while He penetrate C60 cage, the distances of the C’s which are the most adjacent to He are changed with a planar extension and a concerned window is formed; (b) while He penetrate C60 cage, the distances of the C’s which are the most adjacent to He are changed with a spherical extension and a concerned window is formed. The results are given in Figs. 1-2 and Tables 1-2. It is shown that the reaction through path(4) with choice (a) has the least reaction barrier, being optimum. At that case, a window of 9-membered ring is formed. Because the window extension of C6H6 is more free than that of C60, the barrier of He penetrating through C6H6 will be lower than that of He penetrating through C60.     

Topochemical 3D polymerization of C60 under high pressure at elevated temperatures

Fullerene C60 monomer crystals were compressed to a face-centered cubic (fcc) phase with a lattice parameter of a = 11.93(5) A and a micro-Vickers hardness of 4500 kg/mm2 using high-pressure and high-temperature conditions of 15 GPa at 500-600 degrees C. The hardness is compatible with that of cubic boron nitride (c-BN), suggesting the formation of a 3D C60 polymer. The single-crystal X-ray structural analysis revealed that each C60 molecule in the polymer was linked to the 12 nearest neighbors by [2+2] cycloaddition between the common pentagon-hexagon (56) edges. However, ab initio geometry optimization and molecular dynamics calculations suggested that the 3D polymer should have a rhombohedral structure with the space group of R containing [3+3] cycloaddition between the pentagons of C60 molecules within the plane perpendicular to the 3-fold axis. The higher apparent symmetry of fcc was observed as an averaged structure of different orientations of the rhombohedral structure. The R structure can be derived by only a slight rotation of each C60 unit in the (111) plane of the fcc structure. The band-structure calculation suggested that the 3D polymer (R) was a semiconductor; the activation energy for the electrical conductivity was experimentally determined to be 0.25 eV at 550 K.     

Ab initio studies of alkyl radical reactions: Combination and disproportionation reactions of CH3 with C2H5, and the decomposition of chemically activated C3H8

This paper reports the first quantitative ab initio prediction of the disproportionation/combination ratio of alkyl+alkyl reactions using CH3+C2H5 as an example. The reaction has been investigated by the modified Gaussian-2 method with variational transition state or Rice-Ramsperger-Kassel-Marcus calculations for several channels producing (1) CH4+CH2CH2, (2) C3H8, (3) CH4CH3CH, (4) H2+CH3CHCH2, (5) H2+CH3CCH3, and (6) C2H6+CH2 by H-abstraction and association/decomposition mechanisms through singlet and triplet potential energy paths. Significantly, the disproportionation reaction (1) producing CH4+C2H4 was found to occur primarily by the lowest energy path via a loose hydrogen-bonding singlet molecular complex, H3CHC2H4, with a 3.5 kcal/mol binding energy and a small decomposition barrier (1.9 kcal/mol), instead of a direct H-abstraction process. Bimolecular reaction rate constants for the formation of the above products have been calculated in the temperature range 300-3000 K. At 1 atm, formation of C3H8 is dominant below 1200 K. Over 1200 K, the disproportionation reaction becomes competitive. The sum of products (3)-(6) accounts for less than 0.3% below 1500 K and it reaches around 1%-4% above 2000 K. The predicted rate constant for the disproportionation reaction with multiple reflections above the complex well, k1=5.04 x T(0.41) exp(429/T) at 200-600 K and k1=1.96 x 10(-20) T(2.45) exp(1470/T) cm3 molecule(-1) s(-1) at 600-3000 K, agrees closely with experimental values. Similarly, the predicted high-pressure rate constants for the combination reaction forming C3H8 and its reverse dissociation reaction in the temperature range 300-3000 K, k2(infinity)=2.41 x 10(-10) T(-0.34) exp(259/T) cm3 molecule(-1) s(-1) and k(-2)(infinity)=8.89 x 10(22) T(-1.67)exp(-46 037/T) s(-1), respectively, are also in good agreement with available experimental data.     

Quenching of highly vibrationally excited pyrimidine by collisions with CO2

Relaxation of highly vibrationally excited pyrimidine (C(4)N(2)H(4)) by collisions with carbon dioxide has been investigated using diode laser transient absorption spectroscopy. Vibrationally hot pyrimidine (E(')=40 635 cm(-1)) was prepared by 248-nm excimer laser excitation, followed by rapid radiationless relaxation to the ground electronic state. The nascent rotational population distribution (J=58-80) of the 00(0)0 ground state of CO(2) resulting from collisions with hot pyrimidine was probed at short times following the excimer laser pulse. Doppler spectroscopy was used to measure the CO(2) recoil velocity distribution for J=58-80 of the 00(0)0 state. Rate constants and probabilities for collisions populating these CO(2) rotational states were determined. The measured energy transfer probabilities, indexed by final bath state, were resorted as a function of DeltaE to create the energy transfer distribution function, P(E,E(')), from E(')-E approximately 1300-7000 cm(-1). P(E,E(')) is fitted to a single exponential and a biexponential function to determine the average energy transferred in a single collision between pyrimidine and CO(2) and parameters that can be compared to previously studied systems using this technique, pyrazineCO(2), C(6)F(6)CO(2), and methylpyrazineCO(2). P(E,E(')) parameters for these four systems are also compared to various molecular properties of the donor molecules. Finally, P(E,E(')) is analyzed in the context of two models, one which suggests that the shape of P(E,E(')) is primarily determined by the low-frequency out-of-plane donor vibrational modes and one which suggests that the shape of P(E,E(')) can be determined by how the donor molecule final density of states changes with DeltaE.     

Adsorption of CO and O2 on W2C(0001)

CO, O(2), and H(2) adsorption on a clean W(2)C(0001)√13×√13 R ± 13.9° reconstructed surface at room temperature (RT) were investigated using high-resolution electron energy loss spectroscopy (HREELS). The W(2)C(0001) adsorbs CO molecularly and adsorbs O(2) dissociatively, but does not adsorb H(2) at RT. In the CO adsorption system, two C-O stretching (antisymmetric CCO stretching) modes were found at 242.3 meV (1954 cm(-1)) and at 253.0 meV (2041 cm(-1)). The low-frequency site is occupied at first with subsequent conversion to the high-frequency site with increasing coverage. Additionally, a small peak was apparent at 104.5 meV (843 cm(-1)), and a middle peak at 50-51 meV (400-410 cm(-1)), which are assignable to a symmetric stretching mode and a hindered translational mode, respectively, of a CCO (ketenylidene) species. These observations are consistent with the CO adsorption model on top of the surface carbon. For oxygen adsorption, two adsorption states were found at 65.2-68.1 meV (526-549 cm(-1)) and 73.6 meV (594 cm(-1)): typical frequencies to oxygen adsorption on metal surfaces. Results suggest that atomic oxygen adsorption occurred on a threefold hollow site of the second W layer.     

Neutral and ionic complexes of C60 with metal dibenzyldithiocarbamates. Reversible dimerization of C60*- in ionic multicomponent complex [Cr(I)(C6H6)2*+].(C60*-).0.5[Pd(dbdtc)2

New molecular complexes of C60 with metal(II) dibenzyldithiocarbamates, M(dbdtc)2.C60.0.5(C6H5Cl), where M=Cu(II), Ni(II), Pd(II), and Pt(II) and an ionic multicomponent complex [Cr(I)(C6H6)2*+].(C60*-).0.5[Pd(dbdtc)2] (Cr(C6H6)2: bis(benzene)chromium) were obtained. According to IR, UV-visible-NIR, and EPR spectra, involve neutral components, whereas 5 comprises neutral Pd(dbdtc)2 and C60*- and Cr(I)(C6H6)2*+ radical ions. The crystal structure of at 90 K reveals strongly puckered fullerene layers alternating with those composed of Pd(dbdtc)2. The Cr(I)(C6H6)2*+ radical cations are arranged between the layers. Fullerene radical anions form pairs within the layer with an interfullerene C...C contact of 3.092(2) A, indicating their monomeric state at 90 K. This contact is essentially shorter than the sum of van der Waals radii of two carbon atoms, and consequently, C60*- can dimerize. According to SQUID and EPR, single-bonded diamagnetic (C60-)2 dimers form in below 150-130 K on slow cooling and dissociate above 150-170 K on heating. The hysteresis was estimated to be 20 K. For the (C60-)2 dimers in, the dissociation temperature is the lowest among those for ionic complexes of C60 (160-250 K). Fast cooling of the crystals within 10 min from room temperature down to 100 K shifts dimerization temperatures to lower than 60 K. This shift is responsible for the retention of a monomeric phase of at 90 K in the X-ray diffraction experiment.     

Theoretical study of the C6H3 potential energy surface and rate constants and product branching ratios of the C2H(2Sigma+) + C4H2(1Sigma(g)+) and C4H(2Sigma+) + C2H2(1Sigma(g)+) reactions

Ab initio CCSD(T)cc-pVTZ//B3LYP6-311G(**) and CCSD(T)/complete basis set (CBS) calculations of stationary points on the C(6)H(3) potential energy surface have been performed to investigate the reaction mechanism of C(2)H with diacetylene and C(4)H with acetylene. Totally, 25 different C(6)H(3) isomers and 40 transition states are located and all possible bimolecular decomposition products are also characterized. 1,2,3- and 1,2,4-tridehydrobenzene and H(2)CCCCCCH isomers are found to be the most stable thermodynamically residing 77.2, 75.1, and 75.7 kcal/mol lower in energy than C(2)H + C(4)H(2), respectively, at the CCSD(T)/CBS level of theory. The results show that the most favorable C(2)H + C(4)H(2) entrance channel is C(2)H addition to a terminal carbon of C(4)H(2) producing HCCCHCCCH, 70.2 kcal/mol below the reactants. This adduct loses a hydrogen atom from the nonterminal position to give the HCCCCCCH (triacetylene) product exothermic by 29.7 kcal/mol via an exit barrier of 5.3 kcal/mol. Based on Rice-Ramsperger-Kassel-Marcus calculations under single-collision conditions, triacetylene+H are concluded to be the only reaction products, with more than 98% of them formed directly from HCCCHCCCH. The C(2)H + C(4)H(2) reaction rate constants calculated by employing canonical variational transition state theory are found to be similar to those for the related C(2)H + C(2)H(2) reaction in the order of magnitude of 10(-10) cm(3) molecule(-1) s(-1) for T = 298-63 K, and to show a negative temperature dependence at low T. A general mechanism for the growth of polyyne chains involving C(2)H + H(C[triple bond]C)(n)H --> H(C[triple bond]C)(n+1)H + H reactions has been suggested based on a comparison of the reactions of ethynyl radical with acetylene and diacetylene. The C(4)H + C(2)H(2) reaction is also predicted to readily produce triacetylene + H via barrierless C(4)H addition to acetylene, followed by H elimination.     

Computational study on the mechanism and rate constant for the C6H5 + C6H5NO reaction

The reaction mechanism of C6H5 + C6H5NO involving four product channels on the doublet-state potential energy surface has been studied at the B3LYP/6-31+G(d, p) level of theory. The first reaction channel occurs by barrierless association forming (C6H5)2NO (biphenyl nitroxide), which can undergo isomerization and decomposition. The second channel takes place by substitution reaction producing C12H10 (biphenyl) and NO. The third and fourth channels involve direct hydrogen abstraction reactions producing C6H4NO + C6H6 and C6H5NOH + C6H4, respectively. Bimolecular rate constants of the above four product channels have been calculated in the temperature range 300-2000 K by the microcanonical Rice-Ramsperger-Kassel-Marcus theory and/or variational transition-state theory. The result shows the dominant reactions are channel 1 at lower temperatures (T < 800 K) and channel 3 at higher temperatures (T > 800 K). The total rate constant at 7 Torr He is predicted to be k(t) = 3.94 x 10(21) T(-3.09) exp(-699/T) for 300-500 K, 2.09 x 10(20) T(-3.56) exp(2315/T) for 500-1000 K, and 1.51 x 10(2) T(3.30) exp(-3043/T) for 1000-2000 K (in units of cm3 mol(-1) s(-1)), agreeing reasonably with the experimental data within their reported errors. The heats of formation of key products including biphenyl nitroxide, hydroxyl phenyl amino radical, and N-hydroxyl carbazole have been estimated.     

Lifetimes of C60(2-) and C70(2-) dianions in a storage ring

C60(2-) and C70(2-) dianions have been produced by electrospray of the monoanions and subsequent electron pickup in a Na vapor cell. The dianions were stored in an electrostatic ring and their decay by electron emission was measured up to 1 s after injection. While C70(2-) ions are stable on this time scale, except for a small fraction of the ions which have been excited by gas collisions, most of the C60(2-) ions decay on a millisecond time scale, with a lifetime depending strongly on their internal temperature. The results can be modeled as decay by electron tunneling through a Coulomb barrier, mainly from thermally populated triplet states about 120 meV above a singlet ground state. At times longer than about 100 ms, the absorption of blackbody radiation plays an important role for the decay of initially cold ions. The tunneling rates obtained from the modeling, combined with WKB estimates of the barrier penetration, give a ground-state energy 200+/-30 meV above the energy of the monoanion plus a free electron and a ground-state lifetime of the order of 20 s.