Activation of CO2 by Gadolinium Cation (Gd+): Energetics and Mechanism from Experiment and Theory
- 204 Downloads
The exothermic and barrierless activation of CO2 by the lanthanide gadolinium cation (Gd+) to form GdO+ and CO is investigated in detail using guided ion beam tandem mass spectrometry (GIBMS) and theory. Kinetic energy dependent product ion cross sections from collision-induced dissociation (CID) experiments of GdCO2 + are measured to determine the energetics of OGd+(CO) and Gd+(OCO) intermediates. Modeling these cross sections yields bond dissociation energies (BDEs) for OGd+–CO and Gd+–OCO of 0.57 ± 0.05 and 0.38 ± 0.05 eV, respectively. The OGd+–CO BDE is similar to that previously measured for Gd+–CO, which can be attributed to the comparable electrostatic interaction with CO in both complexes. The Gd+(OCO) adduct is identified from calculations to correspond to an electronically excited state. The thermochemistry here and the recently measured GdO+ BDE allows for the potential energy surface (PES) of the Gd+ reaction with CO2 to be deduced from experiment in some detail. Theoretical calculations are performed for comparison with the experimental thermochemistry and for insight into the electronic states of the GdCO2 + intermediates, transition states, and the reaction mechanism. Although the reaction between ground state Gd+ (10D) and CO2 (1Σg +) reactants to form ground state GdO+ (8Σ−) and CO (1Σ+) products is formally spin-forbidden, calculations indicate that there are octet and dectet surfaces having a small energy gap in the entrance channel, such that they can readily mix. Thereby, the reaction can efficiently proceed along the lowest energy octet surface to yield ground state products, consistent with the experimental observations of an efficient, barrierless process. At high collision energies, the measured GdO+ cross section from the Gd+ reaction with CO2 exhibits a distinct feature, attributed to formation of electronically excited GdO+ products along a single dectet PES in a diabatic and spin-allowed process. Modeling this high-energy feature gives an excitation energy of 3.25 ± 0.16 eV relative to the GdO+ (8Σ−) ground state, in good agreement with calculated excitation energies for GdO+ (10Π, 10Σ−) electronic states. The reactivity of Gd+ with CO2 is compared with the group 3 transition metal cations and other lanthanide cations and periodic trends are discussed.
KeywordsCO2 activation Lanthanides Gadolinium Guided ion beam Bond energies Potential energy surface
The authors thank the U.S. Air Force Office of Scientific Research (FA9550-16-1-0095) for financial support, Professor Kirk A. Peterson for providing the all-electron basis sets, and the Center for High Performance Computing at the University of Utah for generous allocation of computer time. Additionally, some of the more computationally demanding calculations were performed on the large shared-memory cluster at the Pittsburgh Supercomputing Center at Carnegie Mellon University via the Extreme Science and Engineering Discovery Environment (XSEDE), under grant number TG-CHE170012. Christopher McNary is thanked for help with using these resources.
- 43.Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark MJ, Heyd J, Brothers EN, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell AP, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam NJ, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, Gaussian, Inc., WallingfordGoogle Scholar
- 57.Foresman JB, Frisch A (1996) Exploring Chemistry with Electronic Structure Methods. Gaussian, PittsburghGoogle Scholar
- 62.Darwent Bd (1970) Bond Dissociation Energies in Simple Molecules. NSRDS-NBS31, 4:48Google Scholar