Electron Paramagnetic Resonance Characteristics and Crystal Structure of a Tutton Salt Analogue: Copper-Doped Cadmium Creatininium Sulfate

Colaneri, Michael J.; Teat, Simon J.; Vitali, Jacqueline

doi:10.1021/acs.jpca.0c00004

Electron Paramagnetic Resonance Characteristics and Crystal Structure of a Tutton Salt Analogue: Copper-Doped Cadmium Creatininium Sulfate

Journal Article · Thu Feb 20 00:00:00 EST 2020 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.0c00004· OSTI ID:1777953

^[1]; Teat, Simon J. ^[2]; Vitali, Jacqueline ^[3]

State Univ. of New York (SUNY), Old Westbury, NY (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Cleveland State Univ., OH (United States)

Electron paramagnetic resonance and crystallographic studies on copper-doped cadmium creatininium sulfate (CdCrnS) were undertaken to study the characteristics of a copper-hexahydrate complex in an organic analogue of Tutton's salt. X-ray diffraction experiments determined the crystal structure of CdCrnS at both 100 and 298 K. CdCrnS, like Tutton salt, crystallizes in the monoclinic space group P2₁/n. The unit cell contains two cadmium hexahydrate complexes, four creatininium ions, four sulfates, and four additional solvation waters. Both crystallography and EPR find that the doped copper replaces the cadmium in the structure. Single-crystal EPR measurements at room temperature determined the g and copper hyperfine (A^Cu) tensors (principal values: g = 2.437, 2.134, and 2.080 and A^Cu = -327, -84.8, and 7.33 MHz). EPR spectra of the powder at room temperature gave g = 2.448, 2.125, and 2.085 and A^Cu = -315, -75.0, and 35.0 MHz and at 110 K gave g = 2.462, 2.116, and 2.077 and A^Cu = -340, -30.0, and 35.0 MHz. The room-temperature tensors are close to the "rigid lattice limit" values found in copper-doped Tutton salts but with a higher gmin and weaker A^Cu_x coupling than average. A small but measurable temperature dependency of the tensors indicated the presence of a dynamic Jahn-Teller (JT) effect. In addition, the EPR line width changed dramatically with temperature, which is like that found in all copper-doped Tutton crystals. Utilizing the model of Silver-Getz for the g-value variation gave an estimate for the energy difference (δ₁₂ = 640 cm^-1) between the ground and next highest JT configurations. An empirical correlation appears to exist between δ₁₂ and g_min and A^Cu_x for the copper hexahydrates studied in similar crystals. Finally, this suggests a relationship between the amount of unpaired spins in the copper d-orbital x lobe and the gap between wells of the adiabatic potential surface.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1777953

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 11 Vol. 124; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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