R. J. F.
Berger‡
*a,
M.
Repisky
b and
S.
Komorovsky
*b
aChemistry of Materials, Paris-Lodron-University Salzburg, Hellbrunner Str. 34, A-5020 Salzburg, Austria. E-mail: Raphael.Berger@sbg.ac.at
bDepartment of Chemistry University of Tromsø, N-9037 Tromsø, Norway. E-mail: stanislav.komorovsky@uit.no
First published on 23rd July 2015
Magnetically induced probability currents in molecules are studied in relativistic theory. Spin–orbit coupling (SOC) enhances the curvature and gives rise to a previously unobserved current cusp in AuH or small bulge-like distortions in HgH2 at the proton positions. The origin of this curvature is magnetically induced spin-density arising from SOC in the relativistic description.
Not taking SOC into account (computational details are provided in the ESI†), AuH sustains one large gold centered diatropic (inductively weakening the external field B) current loop (see Fig. 1b) with a distinct extension directed to the proton. At the FR level (Fig. 1a) the current topology remains unchanged, however, it appears that the current loops contain considerably more curvature around the atomic cores and most notably a kind of current cusp appears at the position of the proton, which without regarding SOC effects (non-SOC) is passed over by a smooth current. Such a cusp structure in molecular ring currents, to the best of our knowledge is previously unobserved. The current difference plot (FR minus non-SOC, Fig. 1c) shows that this cusp originates solely from SOC, causing a strongly localized ring current around the proton. It can be easily seen that a ring current of suitable orientation when added to a smooth current field with little curvature yields a total current of such a cusp shape. However, it is required that the strength of the ring current contribution in the area of the cusp is approximately constant and equal in strength to the smooth current field contribution. Apparently, these conditions are met in the case of AuH. In a homogeneous magnetic field of 1 T strength the total current of the SOC induced vortex around the hydrogen atom integrates to 1.6 nA (see the ESI† for computational details). This additional diatropic vortex causes an SOC induced high field chemical shift of the proton of about −19 ppm compared to the non-SOC calculation (FR shielding: 54 ppm, non-SOC shielding: 35 ppm). The corresponding difference (FR minus non-SOC) of only the z components of the shielding tensor, which can be directly (without taking into account directional averaging) related to the integrated and plotted jB field, is −30 ppm. To quantify the additional curvature of the current field in the region around the hydrogen atom one can calculate the radius of a circular loop of an infinitely thin wire, causing a field of −30 ppm of 1 T (3.0 × 10−5 T) at the center of the loop (hydrogen atom position) and sustaining a current of 1.6 nA using the Biot–Savart law. This yields a loop radius of 0.35 Å or a curvature (reciprocal radius) of 2.9 Å−1.
At the molecular currents of HgH2 at the non-SOC level of theory (Fig. 1e), we find very similar conditions to those in AuH with the exception that the extension of the currents to the proton positions is slightly more pronounced than in AuH. Going to the full relativistic level of theory we again see that more curvature is introduced into the streamlines (Fig. 1d). Unlike in AuH here a drop-shaped deformation of the currents, directed to the center of the molecule, is induced by SOC effects. Again its origins can be readily seen in the difference plot in Fig. 1f (FR minus non-SOC), showing small SOC induced localized current loops on the proton positions. In contrast to the situation in AuH these additional local current loops in HgH2 are paratropic (inductively enhancing the external field B), leading to drop-shaped perturbations rather than the cusp-shaped ones seen in AuH. An integration (see the ESI† for computational details) of these SOC induced local current vortices yields a local paramagnetic contribution of −1.5 nA (in a magnetic field of 1 T). At the SOC level of theory the isotropic 1H chemical shieldings (10 ppm) are found to be down field shifted by +17 ppm as compared to their non-SOC equivalents (27 ppm). An analogous consideration of the curvature as for AuH yields a loop radius of 0.41 Å or a curvature of 2.4 Å−1.
For an explanation of these findings the following can be considered: jB in a single charged spin-free particle in the NR framework contains a sum of two terms which are conventionally called diamagnetic and paramagnetic terms, together these might be called ‘Pauli-current’§ (jPauliB). In the case of a many-particle system described in an effective single particle picture like HF or Kohn–Sham DFT with the total spin equal to zero, like for example a closed shell molecule, jB reduces to the sum of Pauli-current terms of each particle. In the NR framework there are simple MO selection rules allowing for a prediction and a chemical interpretation of these currents,13,14 and the physics of the NR contribution to the molecular currents appears to be well understood. For systems with non-zero spin, and again in the NR case, jB is the sum of the Pauli-current terms plus a ‘spin-current’ term jspin:
jNRB = jPauliB + jspin | (1) |
jspin = rot μspin | (2) |
μspin = −e/mρspin | (3) |
We are here interested in a fully relativistic description including spin–orbit effects of currents in a magnetic field jFRB for “closed shell” molecules (i.e. singlet states in the NR picture). Treating SOC and B as a perturbation and using an effective one-particle description, it can be shown15 that up to second order terms, the total current
jFRB ≈ jPauliB + jspinB,SOC + jB,scalar | (4) |
jFRB − jnon-SOCB ≈ jspinB,SOC = −(e/m) rot ρspinB,SOC | (5) |
We have developed computational methods to calculate four-component relativistic magnetically induced molecular ring currents. Case studies on AuH and HgH2 illustrate that spin–orbit coupling influences the shape of induced currents leading to intriguing curvature and strongly localized ring current contributions to hydrogen atoms bound to gold and mercury. In this way we have revealed the ring current picture of the HALA effect. SOC induced currents in the magnetic field can be traced back directly to an induced spin-density via a relation resembling Ampères law. In general a non-zero and non-constant spin-density arises in ‘closed shell’ molecules due to the presence of both a magnetic field and SOC.
Footnotes |
† Electronic supplementary information (ESI) available: Computational details. See DOI: 10.1039/c5cc05732a |
‡ Current address: Laboratory for Instruction in Swedish, University of Helsinki, A. I. Virtanens Plats 1, FI-00014 University of Helsinki, Finland. |
§ Alternative definitions of the term ‘Pauli current’ are in use. This one might be justified by the notion that it is the current terms which arise already from the Pauli equation.20,21 |
¶ Which is defined as ρspin = ℏ/2 〈σ〉, integrating over spin coordinates. |
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