Supplementary Information
Figure S1. Product ion spectrum of m/z 268 (a), and that of m/z 303 (b) recorded by tandem
mass spectrometry. A sample of HgCl2 was placed in the source and m/z 268 and 303 ions were
mass isolated and subjected to collision-induced dissociation. The relative abundances of the
observed fragments are in excellent agreement with the theoretically predicted fragmentation
pathways.
1
Figure S2: A HePI mass spectrum recorded from a deposit of pure HgI2 (a), and that obtained
from a HgI2 sample exposed to HCl vapor emanating from TiCl3 (b).
2
Figure S3: A time versus absolute intensity plot recorded under negative-ion generating
conditions (m/z 20 to 350), upon exposure of a deposit of Hg(NO3)2 to a HePI source. The
sample was inserted at the beginning of the experiment, and at 0.9 min it was exposed to HCl
vapor emanating from a TiCl3 vial. The insert shows a mass spectrum obtained by summation
of mass spectral data between 0.9 to 1.3 min, and subtracting background data obtained before
the exposure to HCl vapor.
3
Figure S4: (a) Time versus absolute intensity plot recorded under negative-ion generating
conditions upon exposure of a deposit of HgSO4 to a HePI source. After recording background
spectra (m/z 50 to 400) for 2.0 min, a sample of HgSO4 was introduced to the source. At 5.0
min, an aqueous solution of NaCl was added to the dry deposit. At 6.50 min sample deposit plate
was withdrawn from the source. (b) A mass spectrum obtained by summation of mass spectral
data between 3.0 to 5.0 min and subtraction of background data recorded before 2.0 min. (c) A
mass spectrum obtained by summation of mass spectral data between 5.0 to 6.5 min and
subtraction of background data recorded before 2.0 min.
4
Figure S5: A mass spectrum recorded from a deposit of pure HgS sample exposed to HCl vapor
emanating from TiCl3.
5
Figure S6. HePI mass spectra recorded from solid deposits of Hg(II) acetate (a) and Hg(II)
trifluoroacetate (b) exposed to HCl vapor emanating from solid TiCl3.
6
Figure S7. (a) A time versus absolute intensity plot recorded under negative-ion generating
conditions upon exposure of deposit of HgO to a HePI source. After recording spectra for 1.0
min from HgO, an open vial of TiCl3 was introduced to the source and withdrawn after about 1.8
min. The insertion and withdrawal of the TiCl3 vial were repeated three more times and spectra
were recorded from m/z 20 to 450. (b) A mass spectrum obtained by summation of mass spectral
data between 3.0 to 3.4 min, and subtraction of background data recorded before the exposure to
HCl vapor emanating from solid TiCl3.
7
Figure S8. A mass spectrum recorded from a deposit of pure calomel (Hg2Cl2) under a stream of
desolvation gas at 400°C. A very low signal for HgCl2-• was generated from the pristine sample
(blackened area and inset); however, upon addition of a drop of H2O2, the HgCl2-• signal
intensity increased dramatically, and the HgCl3- signals appeared prominently as well (red).
8
Table S1. Theoretical predictions of Hg-Cl bond length using various basis sets.
Method
Cl basis
RHgCl
Error (Å)
(Å)
Experimental
2.252
B3LYP
aug-cc-pvtz
2.298
0.046
M06
aug-cc-pvtz
2.291
0.039
B97D
aug-cc-pvtz
2.306
0.054
wB97XD
aug-cc-pvtz
2.272
0.020
mPW1PW91
aug-cc-pvtz
2.271
0.019
mPW1PW91
6-311+G(3df)
2.273
0.021
mPW1PW91 aug-cc-pv5z
2.261
0.009
CCSD(T)
aug-cc-pvtz
2.274
0.022
CCSD(T)
aug-cc-pvqz
2.237
-0.015
Table S2. Geometric and electronic properties of HgCl2 and HgCl2-•
Species
HgCl2
-• (I)
-•
HgCl2 (II)
-•
HgCl2 (III)
HgCl2
RHgCl
(Å)
ClHgCl
()
Charge
QHg (e)
Charge
QCl (e)
2.261
180.0
1.138
-0.569
Spin
density
Hg (e)
0.000
Spin
density
Cl (e)
0.000
Electronic configuration
2.628
180.0
0.610
-0.805
0.920
0.040
Hg: 6s1.35d106p0.1; Cl: 3s2.03p5.8
2.581
140.2
0.590
-0.795
0.972
0.014
Hg: 6s1.25d106p0.3; Cl: 3s2.03p5.8
3.369
45.8
-0.013
-0.493
0.000
0.500
Hg: 6s2.05d10; Cl: 3s2.03p5.5
Hg: 6s0.75d9.96p0.2; Cl: 3s1.93p5.6
All calculations were done using Gaussian 09 [1]. Geometries of all species were optimized by
using the mPW1PW91 method, with SDD for Hg [2], and the largest available Dunning’s
correlation consistent basis aug-cc-pv5z for Cl. This is based on the methodological studies
showing in Table S1, evaluating B3LYP [3, 4] and mPW1PW91 [5] based on their good
performance in previous investigations of metal complexes [6-12] and three more recently
developed methods: M06 [13], B97D [14], and wB97xd [15]. Consistent with our previous
reports for transition metal complexes [7, 9-12], the best result is from using mPW1PW91 (Table
S1).
9
Frequency calculations were done to verify the nature of respective species in their potential
energy surfaces, with all positive frequencies found for minimal energy states and only one
imaginary frequency found for the transition state. Gibbs free energies were calculated from
using the mPW1PW91 method, with the CCSD(T) energy correction by adding the difference of
CCSD(T) and mPW1PW91 electronic energies for each species.
References:
1.
Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman,
J. R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G. A., Nakatsuji, H., Caricato,
M., Li, X., Hratchian, H. P., Izmaylov, A. F., Bloino, J., Zheng, G., Sonnenberg, J. L.,
Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T.,
Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, Jr., J. A., J. Peralta, E.,
Ogliaro, F., Bearpark, M., Heyd, J. J., Brothers, E., Kudin, K. N., Staroverov, V. N.,
Keith, T., Kobayashi, R., Normand,J., Raghavachari, K., Rendell, A., Burant, J. C.,
Iyengar, S. S., Tomasi, J., Cossi, M., Rega, N., Millam, J. M., Klene, M., Knox, J. E.,
Cross, J. B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R. E.,
Yazyev, O., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J. W., Martin, R. L.,
Morokuma, K., Zakrzewski,V. G., Voth, G. A., Salvador, P., Dannenberg, J. J., Dapprich,
S., Daniels, A. D., Farkas, O., Foresman, J. B., Ortiz, J. V., Cioslowski, J., Fox, D. J.,
Gaussian 09, Revision B.01; Gaussian, Inc.: Wallingford CT, 2010.
2.
Leininger, T., Nicklass, A., Stoll, H., Dolg, M., Schwerdtfeger, P.: The accuracy of the
pseudopotential approximation. II. A comparison of various core sizes for indium
pseudopotentials in calculations for spectroscopic constants of InH, InF, and InCl J.
Chem. Phys. 105, 1052-1059 (1996)
3.
Becke, A. D.: Density‐functional thermochemistry. III. The role of exact exchange J.
Chem. Phys. 98, 5648-5652 (1993)
4.
Lee, C., Yang, W., Parr, R. G.: Development of the Colle-Salvetti correlation-energy
formula into a functional of the electron density Phys. Rev. B 37, 785-789 (1988).
10
5.
Adamo, C., Barone, V.: Exchange functionals with improved long-range behavior and
adiabatic connection methods without adjustable parameters: The mPW and mPW1PW
models J. Chem. Phys. 108, 664-675 (1998)
6.
Nakamura, E., Yoshikai, N., Yamanaka, M.: Mechanism of C−H bond activation/C−C
bond formation reaction between diazo compound and alkane catalyzed by dirhodium
tetracarboxylate J. Am. Chem. Soc. 124, 7181-7192 (2002)
7.
Zhang, Y., Guo, Z. J., You, X. Z.: Hydrolysis Theory for Cisplatin and Its Analogues
Based on Density Functional Studies J. Am. Chem. Soc. 123, 9378-9387 (2001)
8.
Siegbahn, P. E. M.: The performance of hybrid DFT for mechanisms involving transition
metal complexes in enzymes J. Biol. Inorg. Chem. 11, 695-701 (2006)
9.
Zhang, Y., Lewis, J. C., Bergman, R. G., Ellman, J. A., Oldfield, E.: NMR shifts, orbitals,
and M···H−X bonding in d8 square planar metal complexes Organometallics 25, 35153519 (2006)
10.
Balof, S. L., Yu, B., Lowe, A. B., Ling, Y., Zhang, Y., Schanz, H. J.: Ru-based olefin
metathesis catalysts vearing pH-responsive N-heterocyclic carbene (NHC) ligands:
activity control via degree of protonation Eur. J. Inorg. Chem. 13, 1717-1722 (2009)
11.
Stevenson, S., Ling, Y., Coumbe, C. E., Mackey, M. A., Confait, B. S., Phillips, J. P.,
Dorn, H. C., Zhang, Y.: Preferential encapsulation and stability of La3N cluster in 80
atom Cages: experimental synthesis and computational investigation of La3N@C79N J.
Am. Chem. Soc. 131, 17780-17782 (2009)
12.
Ling, Y., Khade, R. L., Zhang, Y.: Structural, EPR superhyperfine, and NMR hyperfine
properties of the Cu−octarepeat binding site in the prion protein J. Phys. Chem. B 115,
2663-2670 (2011)
13.
Truhlar, D. G., Zhao, Y.: The M06 suite of density functionals for main group
thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and
transition elements: two new functionals and systematic testing of four M06-class
functionals and 12 other functionals Theor. Chem. Acc. 120, 215-241 (2008)
14.
Grimme, S.: Semiempirical GGA-type density functional constructed with a long-range
dispersion correction J. Comp. Chem. 27, 1787-1799 (2006)
11
15.
Chai, J.-D., Head-Gordon, M.: Long-range corrected hybrid density functionals with
damped atom–atom dispersion corrections Phys. Chem. Chem. Phys. 10, 6615-6620
(2008)
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