The Experts below are selected from a list of 59550 Experts worldwide ranked by ideXlab platform
Laszlo Zalavari - One of the best experts on this subject based on the ideXlab platform.
-
point particle effective field theory ii Relativistic Effects and coulomb inverse square competition
Journal of High Energy Physics, 2017Co-Authors: Peter Hayman, C P Burgess, Laszlo Zalavari, Markus Rummel, M P WilliamsAbstract:We apply point-particle effective field theory (PPEFT) to compute the leading shifts due to finite-size source Effects in the Coulomb bound energy levels of a Relativistic spinless charged particle. This is the analogue for spinless electrons of the contribution of the charge-radius of the source to these levels, and we disagree with standard calculations in several ways. Most notably we find there are two effective interactions with the same dimension that contribute to leading order in the nuclear size. One is the standard charge-radius contribution, while the other is a contact interaction whose leading contribution to $\delta E$ arises linearly in the small length scale, $\epsilon$, characterizing the finite-size Effects, and is suppressed by $(Z\alpha)^5$. We argue that standard calculations miss the contributions of this second operator because they err in their choice of boundary conditions at the source for the wave-function of the orbiting particle. PPEFT predicts how this boundary condition depends on the source's charge radius, as well as on the orbiting particle's mass. Its contribution turns out to be crucial if the charge radius satisfies $\epsilon \lesssim (Z\alpha)^2 a_B$, with $a_B$ the Bohr radius, since then Relativistic Effects become important. We show how the problem is equivalent to solving the Schrodinger equation with competing Coulomb, inverse-square and delta-function potentials, which we solve explicitly. A similar enhancement is not predicted for the hyperfine structure, due to its spin-dependence. We show how the charge-radius effectively runs due to classical renormalization Effects, and why the resulting RG flow is central to predicting the size of the energy shifts. We discuss how this flow is relevant to systems having much larger-than-geometric cross sections, and the possible relevance to catalysis of reactions through scattering with monopoles.
-
point particle effective field theory ii Relativistic Effects and coulomb inverse square competition
Journal of High Energy Physics, 2017Co-Authors: Peter Hayman, C P Burgess, Laszlo Zalavari, Markus Rummel, M P WilliamsAbstract:We apply point-particle effective field theory (PPEFT) to compute the leading shifts due to finite-sized source Effects in the Coulomb bound energy levels of a Relativistic spinless charged particle. This is the analogue for spinless electrons of calculating the contribution of the charge-radius of the source to these levels, and our calculation disagrees with standard calculations in several ways. Most notably we find there are two effective interactions with the same dimension that contribute to leading order in the nuclear size, one of which captures the standard charge-radius contribution. The other effective operator is a contact interaction whose leading contribution to δE arises linearly (rather than quadratically) in the small length scale, ϵ, characterizing the finite-size Effects, and is suppressed by (Zα)5. We argue that standard calculations miss the contributions of this second operator because they err in their choice of boundary conditions at the source for the wave-function of the orbiting particle. PPEFT predicts how this boundary condition depends on the source’s charge radius, as well as on the orbiting particle’s mass. Its contribution turns out to be crucial if the charge radius satisfies ϵ ≲ (Zα)2 a B , where a B is the Bohr radius, because then Relativistic Effects become important for the boundary condition. We show how the problem is equivalent to solving the Schrodinger equation with competing Coulomb, inverse-square and delta-function potentials, which we solve explicitly. A similar enhancement is not predicted for the hyperfine structure, due to its spin-dependence. We show how the charge-radius effectively runs due to classical renormalization Effects, and why the resulting RG flow is central to predicting the size of the energy shifts (and is responsible for its being linear in the source size). We discuss how this flow is relevant to systems having much larger-than-geometric cross sections, such as those with large scattering lengths and perhaps also catalysis of reactions through scattering with monopoles. Experimental observation of these Effects would require more precise measurement of energy levels for mesonic atoms than are now possible.
C P Burgess - One of the best experts on this subject based on the ideXlab platform.
-
point particle effective field theory ii Relativistic Effects and coulomb inverse square competition
Journal of High Energy Physics, 2017Co-Authors: Peter Hayman, C P Burgess, Laszlo Zalavari, Markus Rummel, M P WilliamsAbstract:We apply point-particle effective field theory (PPEFT) to compute the leading shifts due to finite-size source Effects in the Coulomb bound energy levels of a Relativistic spinless charged particle. This is the analogue for spinless electrons of the contribution of the charge-radius of the source to these levels, and we disagree with standard calculations in several ways. Most notably we find there are two effective interactions with the same dimension that contribute to leading order in the nuclear size. One is the standard charge-radius contribution, while the other is a contact interaction whose leading contribution to $\delta E$ arises linearly in the small length scale, $\epsilon$, characterizing the finite-size Effects, and is suppressed by $(Z\alpha)^5$. We argue that standard calculations miss the contributions of this second operator because they err in their choice of boundary conditions at the source for the wave-function of the orbiting particle. PPEFT predicts how this boundary condition depends on the source's charge radius, as well as on the orbiting particle's mass. Its contribution turns out to be crucial if the charge radius satisfies $\epsilon \lesssim (Z\alpha)^2 a_B$, with $a_B$ the Bohr radius, since then Relativistic Effects become important. We show how the problem is equivalent to solving the Schrodinger equation with competing Coulomb, inverse-square and delta-function potentials, which we solve explicitly. A similar enhancement is not predicted for the hyperfine structure, due to its spin-dependence. We show how the charge-radius effectively runs due to classical renormalization Effects, and why the resulting RG flow is central to predicting the size of the energy shifts. We discuss how this flow is relevant to systems having much larger-than-geometric cross sections, and the possible relevance to catalysis of reactions through scattering with monopoles.
-
point particle effective field theory ii Relativistic Effects and coulomb inverse square competition
Journal of High Energy Physics, 2017Co-Authors: Peter Hayman, C P Burgess, Laszlo Zalavari, Markus Rummel, M P WilliamsAbstract:We apply point-particle effective field theory (PPEFT) to compute the leading shifts due to finite-sized source Effects in the Coulomb bound energy levels of a Relativistic spinless charged particle. This is the analogue for spinless electrons of calculating the contribution of the charge-radius of the source to these levels, and our calculation disagrees with standard calculations in several ways. Most notably we find there are two effective interactions with the same dimension that contribute to leading order in the nuclear size, one of which captures the standard charge-radius contribution. The other effective operator is a contact interaction whose leading contribution to δE arises linearly (rather than quadratically) in the small length scale, ϵ, characterizing the finite-size Effects, and is suppressed by (Zα)5. We argue that standard calculations miss the contributions of this second operator because they err in their choice of boundary conditions at the source for the wave-function of the orbiting particle. PPEFT predicts how this boundary condition depends on the source’s charge radius, as well as on the orbiting particle’s mass. Its contribution turns out to be crucial if the charge radius satisfies ϵ ≲ (Zα)2 a B , where a B is the Bohr radius, because then Relativistic Effects become important for the boundary condition. We show how the problem is equivalent to solving the Schrodinger equation with competing Coulomb, inverse-square and delta-function potentials, which we solve explicitly. A similar enhancement is not predicted for the hyperfine structure, due to its spin-dependence. We show how the charge-radius effectively runs due to classical renormalization Effects, and why the resulting RG flow is central to predicting the size of the energy shifts (and is responsible for its being linear in the source size). We discuss how this flow is relevant to systems having much larger-than-geometric cross sections, such as those with large scattering lengths and perhaps also catalysis of reactions through scattering with monopoles. Experimental observation of these Effects would require more precise measurement of energy levels for mesonic atoms than are now possible.
Markus Rummel - One of the best experts on this subject based on the ideXlab platform.
-
point particle effective field theory ii Relativistic Effects and coulomb inverse square competition
Journal of High Energy Physics, 2017Co-Authors: Peter Hayman, C P Burgess, Laszlo Zalavari, Markus Rummel, M P WilliamsAbstract:We apply point-particle effective field theory (PPEFT) to compute the leading shifts due to finite-size source Effects in the Coulomb bound energy levels of a Relativistic spinless charged particle. This is the analogue for spinless electrons of the contribution of the charge-radius of the source to these levels, and we disagree with standard calculations in several ways. Most notably we find there are two effective interactions with the same dimension that contribute to leading order in the nuclear size. One is the standard charge-radius contribution, while the other is a contact interaction whose leading contribution to $\delta E$ arises linearly in the small length scale, $\epsilon$, characterizing the finite-size Effects, and is suppressed by $(Z\alpha)^5$. We argue that standard calculations miss the contributions of this second operator because they err in their choice of boundary conditions at the source for the wave-function of the orbiting particle. PPEFT predicts how this boundary condition depends on the source's charge radius, as well as on the orbiting particle's mass. Its contribution turns out to be crucial if the charge radius satisfies $\epsilon \lesssim (Z\alpha)^2 a_B$, with $a_B$ the Bohr radius, since then Relativistic Effects become important. We show how the problem is equivalent to solving the Schrodinger equation with competing Coulomb, inverse-square and delta-function potentials, which we solve explicitly. A similar enhancement is not predicted for the hyperfine structure, due to its spin-dependence. We show how the charge-radius effectively runs due to classical renormalization Effects, and why the resulting RG flow is central to predicting the size of the energy shifts. We discuss how this flow is relevant to systems having much larger-than-geometric cross sections, and the possible relevance to catalysis of reactions through scattering with monopoles.
-
point particle effective field theory ii Relativistic Effects and coulomb inverse square competition
Journal of High Energy Physics, 2017Co-Authors: Peter Hayman, C P Burgess, Laszlo Zalavari, Markus Rummel, M P WilliamsAbstract:We apply point-particle effective field theory (PPEFT) to compute the leading shifts due to finite-sized source Effects in the Coulomb bound energy levels of a Relativistic spinless charged particle. This is the analogue for spinless electrons of calculating the contribution of the charge-radius of the source to these levels, and our calculation disagrees with standard calculations in several ways. Most notably we find there are two effective interactions with the same dimension that contribute to leading order in the nuclear size, one of which captures the standard charge-radius contribution. The other effective operator is a contact interaction whose leading contribution to δE arises linearly (rather than quadratically) in the small length scale, ϵ, characterizing the finite-size Effects, and is suppressed by (Zα)5. We argue that standard calculations miss the contributions of this second operator because they err in their choice of boundary conditions at the source for the wave-function of the orbiting particle. PPEFT predicts how this boundary condition depends on the source’s charge radius, as well as on the orbiting particle’s mass. Its contribution turns out to be crucial if the charge radius satisfies ϵ ≲ (Zα)2 a B , where a B is the Bohr radius, because then Relativistic Effects become important for the boundary condition. We show how the problem is equivalent to solving the Schrodinger equation with competing Coulomb, inverse-square and delta-function potentials, which we solve explicitly. A similar enhancement is not predicted for the hyperfine structure, due to its spin-dependence. We show how the charge-radius effectively runs due to classical renormalization Effects, and why the resulting RG flow is central to predicting the size of the energy shifts (and is responsible for its being linear in the source size). We discuss how this flow is relevant to systems having much larger-than-geometric cross sections, such as those with large scattering lengths and perhaps also catalysis of reactions through scattering with monopoles. Experimental observation of these Effects would require more precise measurement of energy levels for mesonic atoms than are now possible.
Peter Hayman - One of the best experts on this subject based on the ideXlab platform.
-
point particle effective field theory ii Relativistic Effects and coulomb inverse square competition
Journal of High Energy Physics, 2017Co-Authors: Peter Hayman, C P Burgess, Laszlo Zalavari, Markus Rummel, M P WilliamsAbstract:We apply point-particle effective field theory (PPEFT) to compute the leading shifts due to finite-size source Effects in the Coulomb bound energy levels of a Relativistic spinless charged particle. This is the analogue for spinless electrons of the contribution of the charge-radius of the source to these levels, and we disagree with standard calculations in several ways. Most notably we find there are two effective interactions with the same dimension that contribute to leading order in the nuclear size. One is the standard charge-radius contribution, while the other is a contact interaction whose leading contribution to $\delta E$ arises linearly in the small length scale, $\epsilon$, characterizing the finite-size Effects, and is suppressed by $(Z\alpha)^5$. We argue that standard calculations miss the contributions of this second operator because they err in their choice of boundary conditions at the source for the wave-function of the orbiting particle. PPEFT predicts how this boundary condition depends on the source's charge radius, as well as on the orbiting particle's mass. Its contribution turns out to be crucial if the charge radius satisfies $\epsilon \lesssim (Z\alpha)^2 a_B$, with $a_B$ the Bohr radius, since then Relativistic Effects become important. We show how the problem is equivalent to solving the Schrodinger equation with competing Coulomb, inverse-square and delta-function potentials, which we solve explicitly. A similar enhancement is not predicted for the hyperfine structure, due to its spin-dependence. We show how the charge-radius effectively runs due to classical renormalization Effects, and why the resulting RG flow is central to predicting the size of the energy shifts. We discuss how this flow is relevant to systems having much larger-than-geometric cross sections, and the possible relevance to catalysis of reactions through scattering with monopoles.
-
point particle effective field theory ii Relativistic Effects and coulomb inverse square competition
Journal of High Energy Physics, 2017Co-Authors: Peter Hayman, C P Burgess, Laszlo Zalavari, Markus Rummel, M P WilliamsAbstract:We apply point-particle effective field theory (PPEFT) to compute the leading shifts due to finite-sized source Effects in the Coulomb bound energy levels of a Relativistic spinless charged particle. This is the analogue for spinless electrons of calculating the contribution of the charge-radius of the source to these levels, and our calculation disagrees with standard calculations in several ways. Most notably we find there are two effective interactions with the same dimension that contribute to leading order in the nuclear size, one of which captures the standard charge-radius contribution. The other effective operator is a contact interaction whose leading contribution to δE arises linearly (rather than quadratically) in the small length scale, ϵ, characterizing the finite-size Effects, and is suppressed by (Zα)5. We argue that standard calculations miss the contributions of this second operator because they err in their choice of boundary conditions at the source for the wave-function of the orbiting particle. PPEFT predicts how this boundary condition depends on the source’s charge radius, as well as on the orbiting particle’s mass. Its contribution turns out to be crucial if the charge radius satisfies ϵ ≲ (Zα)2 a B , where a B is the Bohr radius, because then Relativistic Effects become important for the boundary condition. We show how the problem is equivalent to solving the Schrodinger equation with competing Coulomb, inverse-square and delta-function potentials, which we solve explicitly. A similar enhancement is not predicted for the hyperfine structure, due to its spin-dependence. We show how the charge-radius effectively runs due to classical renormalization Effects, and why the resulting RG flow is central to predicting the size of the energy shifts (and is responsible for its being linear in the source size). We discuss how this flow is relevant to systems having much larger-than-geometric cross sections, such as those with large scattering lengths and perhaps also catalysis of reactions through scattering with monopoles. Experimental observation of these Effects would require more precise measurement of energy levels for mesonic atoms than are now possible.
Ghosh Abhik - One of the best experts on this subject based on the ideXlab platform.
-
Relativistic Effects on a Metal-Metal Bond: Osmium Corrole Dimers.
eScholarship University of California, 2019Co-Authors: Alemayehu, Abraham B, Mccormick, Laura J, Vazquez-lima Hugo, Ghosh AbhikAbstract:A series of metal-metal bonded osmium corrole dimers, {Os[T pXPC]}2, were synthesized in reasonably good yields (35-46%) via the interaction of the corresponding free-base meso-tris( p-X-phenyl)corroles (H3[T pXPC], X = CF3, H, CH3, and OCH3), Os3(CO)12, and potassium carbonate in 1,2,4-trichlorobenzene under an inert atmosphere at 180 °C over several hours. The complexes are only the second class of Os corroles reported to date (the first being OsVIN corroles) and also the second class of metal-metal bonded metallocorrole dimers (the other being Ru corrole dimers). Comparison of the X-ray structures, redox potentials, and optical spectra of analogous Ru and Os corrole dimers, along with scalar-Relativistic DFT calculations, has provided an experimentally calibrated account of Relativistic Effects in these complexes. Three of the Os corrole dimers (X = CF3, H, and OCH3) were analyzed with single-crystal X-ray diffraction analysis, revealing inversion-related corrole rings with eclipsed Os-N bonds and Os-Os distances of ∼2.24 Å that are ∼0.06 Å longer than the Ru-Ru distances in the analogous Ru corrole dimers. Interestingly, a comparison of scalar-Relativistic and nonRelativistic DFT calculations indicates that this difference in metal-metal bond distance does not, in fact, reflect a differential Relativistic effect. For a given corrole ligand, the Ru and Os corrole dimers exhibit nearly identical oxidation potentials but dramatically different reduction potentials, with the Os values ∼0.5 V lower relative to Ru, suggesting that whereas oxidation occurs in a ligand-centered manner, reduction is substantially metal-centered, which indeed was confirmed by scalar-Relativistic calculations. The calculations further indicate that approximately a third of the ∼0.5 V difference in reduction potentials can be ascribed to relativity. The somewhat muted value of this Relativistic effect appears to be related to the finding that reduction of an Os corrole dimer is not exclusively metal-based but that a significant amount of spin density is delocalized over to the corrole ligand; in contrast, reduction of an Ru corrole dimer occurs exclusively on the Ru-Ru linkage. For isoelectronic complexes, the Ru and Os corrole dimers exhibit substantially different UV-vis spectra. A key difference is a strong near-UV feature of the Os series, which in energy terms is blue-shifted by ∼0.55 V relative to the analogous feature of the Ru series. TDDFT calculations suggest that this difference may be related to higher-energy Os(5d)-based LUMOs in the Os case relative to analogous MOs for Ru
-
Relativistic Effects on a Metal-Metal Bond: Osmium Corrole Dimers
'American Chemical Society (ACS)', 2019Co-Authors: Alemayehu Abraham, Mccormick, Laura J, Vazquez-lima Hugo, Ghosh AbhikAbstract:Publisher's statement (option C): https://pubs.acs.org/page/4authors/authorchoice/options.htmlA series of metal–metal bonded osmium corrole dimers, {Os[TpXPC]}2, were synthesized in reasonably good yields (35–46%) via the interaction of the corresponding free-base meso-tris(p-X-phenyl)corroles (H3[TpXPC], X = CF3, H, CH3, and OCH3), Os3(CO)12, and potassium carbonate in 1,2,4-trichlorobenzene under an inert atmosphere at 180 °C over several hours. The complexes are only the second class of Os corroles reported to date (the first being OsVIN corroles) and also the second class of metal–metal bonded metallocorrole dimers (the other being Ru corrole dimers). Comparison of the X-ray structures, redox potentials, and optical spectra of analogous Ru and Os corrole dimers, along with scalar-Relativistic DFT calculations, has provided an experimentally calibrated account of Relativistic Effects in these complexes. Three of the Os corrole dimers (X = CF3, H, and OCH3) were analyzed with single-crystal X-ray diffraction analysis, revealing inversion-related corrole rings with eclipsed Os–N bonds and Os–Os distances of ∼2.24 Å that are ∼0.06 Å longer than the Ru–Ru distances in the analogous Ru corrole dimers. Interestingly, a comparison of scalar-Relativistic and nonRelativistic DFT calculations indicates that this difference in metal–metal bond distance does not, in fact, reflect a differential Relativistic effect. For a given corrole ligand, the Ru and Os corrole dimers exhibit nearly identical oxidation potentials but dramatically different reduction potentials, with the Os values ∼0.5 V lower relative to Ru, suggesting that whereas oxidation occurs in a ligand-centered manner, reduction is substantially metal-centered, which indeed was confirmed by scalar-Relativistic calculations. The calculations further indicate that approximately a third of the ∼0.5 V difference in reduction potentials can be ascribed to relativity. The somewhat muted value of this Relativistic effect appears to be related to the finding that reduction of an Os corrole dimer is not exclusively metal-based but that a significant amount of spin density is delocalized over to the corrole ligand; in contrast, reduction of an Ru corrole dimer occurs exclusively on the Ru–Ru linkage. For isoelectronic complexes, the Ru and Os corrole dimers exhibit substantially different UV–vis spectra. A key difference is a strong near-UV feature of the Os series, which in energy terms is blue-shifted by ∼0.55 V relative to the analogous feature of the Ru series. TDDFT calculations suggest that this difference may be related to higher-energy Os(5d)-based LUMOs in the Os case relative to analogous MOs for Ru
-
Rare and Nonexistent Nitrosyls: Periodic Trends and Relativistic Effects in Ruthenium and Osmium Porphyrin-Based {MNO}7 Complexes
'American Chemical Society (ACS)', 2018Co-Authors: Demissie, Taye Beyene, Ruud Kenneth, Vazquez-lima Hugo, Conradie Jeanet, Ghosh AbhikAbstract:The following article: Demissie, T.B., Conradie, J., Vazquez-Lima, H., Ruud, K. & Ghosh, A. (2018). Rare and Nonexistent Nitrosyls: Periodic Trends and Relativistic Effects in Ruthenium and Osmium Porphyrin-Based {MNO}7 Complexes. ACS Omega, 3(9), 10513-10516 can be accessed at https://doi.org/10.1021/acsomega.8b01434. c. Licensed CC BY-NC-ND 4.0.Relativistic and nonRelativistic density functional theory calculations were used to investigate rare or nonexistent ruthenium and osmium analogues of nitrosylhemes. Strong ligand field Effects and, to a lesser degree, Relativistic Effects were found to destabilize {RuNO}7 porphyrins relative to their {FeNO}7 analogues. Substantially stronger Relativistic Effects account for the even greater instability and/or nonexistence of {OsNO}7 porphyrin derivatives
-
Stepwise Deoxygenation of Nitrite as a Route to Two Families of Ruthenium Corroles: Group 8 Periodic Trends and Relativistic Effects
'American Chemical Society (ACS)', 2017Co-Authors: Alemayehu Abraham, Gagnon, Kevin J, Vazquez-lima Hugo, Ghosh AbhikAbstract:This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.7b00377.Given the many applications of ruthenium porphyrins, the rarity of ruthenium corroles and the underdeveloped state of their chemistry are clearly indicative of an area ripe for significant breakthroughs. The tendency of ruthenium corroles to form unreactive metal–metal-bonded dimers has been recognized as a key impediment in this area. Herein, by exposing free-base meso-tris(p-X-phenyl)corroles, H3[TpXPC] (X = CF3, H, Me, and OMe), and [Ru(COD)Cl2]x in refluxing 2-methoxyethanol to nitrite, we have been able to reliably intercept the series Ru[TpXPC](NO) in a matter of seconds to minutes and subsequently RuVI[TpXPC](N), the products of a second deoxygenation, over some 16 h. Two of the RuVIN complexes and one ruthenium corrole dimer could be crystallographically analyzed; the Ru–Nnitrido distance was found to be ∼1.61 Å, consistent with the triple-bonded character of the RuVIN units and essentially identical with the Os–Nnitrido distance in analogous osmium corroles. Spectroscopic and density functional theory (DFT) calculations suggest that the RuNO corroles are best viewed as innocent {RuNO}6 complexes, whereas the analogous FeNO corroles are noninnocent, i.e., best viewed as {FeNO}7-corrole•2–. Both RuVIN and OsVIN corroles exhibit sharp Soret bands, suggestive of an innocent macrocycle. A key difference between the two metals is that the Soret maxima of the OsVIN corroles are red-shifted some 25 nm relative to those of the RuVIN complexes. Careful time-dependent DFT studies indicate that this difference is largely attributable to Relativistic Effects in OsVIN corroles. The availability of two new classes of mononuclear ruthenium corroles potentially opens the door to new applications, in such areas as catalysis and cancer therapy
-
Stepwise Deoxygenation of Nitrite as a Route to Two Families of Ruthenium Corroles: Group 8 Periodic Trends and Relativistic Effects
American Chemical Society, 2017Co-Authors: Alemayehu Abraham, Gagnon, Kevin J, Vazquez-lima Hugo, Ghosh AbhikAbstract:Given the many applications of ruthenium porphyrins, the rarity of ruthenium corroles and the underdeveloped state of their chemistry are clearly indicative of an area ripe for significant breakthroughs. The tendency of ruthenium corroles to form unreactive metal–metal-bonded dimers has been recognized as a key impediment in this area. Herein, by exposing free-base meso-tris(p-X-phenyl)corroles, H3[TpXPC] (X = CF3, H, Me, and OMe), and [Ru(COD)Cl2]x in refluxing 2-methoxyethanol to nitrite, we have been able to reliably intercept the series Ru[TpXPC](NO) in a matter of seconds to minutes and subsequently RuVI[TpXPC](N), the products of a second deoxygenation, over some 16 h. Two of the RuVIN complexes and one ruthenium corrole dimer could be crystallographically analyzed; the Ru–Nnitrido distance was found to be ∼1.61 Å, consistent with the triple-bonded character of the RuVIN units and essentially identical with the Os–Nnitrido distance in analogous osmium corroles. Spectroscopic and density functional theory (DFT) calculations suggest that the RuNO corroles are best viewed as innocent {RuNO}6 complexes, whereas the analogous FeNO corroles are noninnocent, i.e., best viewed as {FeNO}7-corrole•2–. Both RuVIN and OsVIN corroles exhibit sharp Soret bands, suggestive of an innocent macrocycle. A key difference between the two metals is that the Soret maxima of the OsVIN corroles are red-shifted some 25 nm relative to those of the RuVIN complexes. Careful time-dependent DFT studies indicate that this difference is largely attributable to Relativistic Effects in OsVIN corroles. The availability of two new classes of mononuclear ruthenium corroles potentially opens the door to new applications, in such areas as catalysis and cancer therapy
