All–Metal Aromaticity: Revisiting the Ring Current Model among
Transition Metal Clusters

J 2013

All–Metal Aromaticity: Revisiting the Ring Current Model among Transition Metal Clusters

BADRI, Zahra, Shubhrodeep PATHAK, Heike FLIEGL, Parviz RASHIDI-RANJBAR, Radovan BAST et. al.

Základní údaje

Originální název

All–Metal Aromaticity: Revisiting the Ring Current Model among Transition Metal Clusters

Autoři

BADRI, Zahra (364 Írán, domácí), Shubhrodeep PATHAK (356 Indie), Heike FLIEGL (578 Norsko), Parviz RASHIDI-RANJBAR (364 Írán), Radovan BAST (250 Francie), Radek MAREK (203 Česká republika, garant, domácí), Cina FOROUTANNEJAD (364 Írán, domácí) a Kenneth RUUD (578 Norsko)

Vydání

Journal of Chemical Theory and Computation, Washington, American Chemical Society, 2013, 1549-9618

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10403 Physical chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

DOI: 10.1021/ct4007184

Impakt faktor

Impact factor: 5.310

Kód RIV

RIV/00216224:14740/13:00066466

Organizační jednotka

Středoevropský technologický institut

DOI

http://dx.doi.org/10.1021/ct4007184

UT WoS

000327044500013

Klíčová slova anglicky

Ring Current Model; Magnetizability; All-Metal Aromaticity; DFT; MCSCF

Štítky

rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 1. 10. 2014 11:33, prof. RNDr. Radek Marek, Ph.D.

Anotace

V originále

We present new insight into the nature of aromaticity in metal clusters. We give computational arguments in favor of using the ring-current model over local indices, such as nucleus independent chemical shifts, for the determination of the magnetic aromaticity. Two approaches for estimating magnetically induced ring currents are employed for this purpose; one based on the quantum theory of atoms in molecules (QTAIM) and the other where magnetically–induced current densities (MICD) are explicitly calculated. We show that the two–zone aromaticity/antiaromaticity of a number of 3d metallic clusters (Sc3–, Cu3+, and Cu42–) can be explained using the QTAIM–based magnetizabilities. The reliability of the calculated atomic and bond magnetizabilities of the metallic clusters are verified by comparison with MICD computed at the multiconfiguration self–consistent field (MCSCF) and density functional levels of theory. Integrated MCSCF current strength susceptibilities as well as a visual analysis of the calculated current densities confirm the interpretations based on the QTAIM magnetizabilities. In view of the new findings, we suggest a simple explanation based on classical electromagnetic theory to explain the anomalous magnetic shielding in different transition metal clusters. Our results suggest that the nature of magnetic aromaticity/antiaromaticity in transition–metal clusters should be assessed more carefully based on global indices.

Návaznosti

ED1.1.00/02.0068, projekt VaV

Název: CEITEC - central european institute of technology

EE2.3.30.0009, projekt VaV

Název: Zaměstnáním čerstvých absolventů doktorského studia k vědecké excelenci

GAP206/12/0539, projekt VaV

Název: Struktura a dynamika komplexů přechodných kovů a jejich interakce s kavitandy (Akronym: METALIN)

Investor: Grantová agentura ČR, Struktura a dynamika komplexů přechodných kovů a jejich interakce s kavitandy

Přiložené soubory

JCTC13_9_4789_ct4007184.pdf

Požádat o autorskou verzi souboru

Citovat

BADRI, Zahra, Shubhrodeep PATHAK, Heike FLIEGL, Parviz RASHIDI-RANJBAR, Radovan BAST, Radek MAREK, Cina FOROUTANNEJAD a Kenneth RUUD. All–Metal Aromaticity: Revisiting the Ring Current Model among Transition Metal Clusters. Journal of Chemical Theory and Computation. Washington: American Chemical Society, 2013, roč. 9, č. 11, s. 4789-4796. ISSN 1549-9618. Dostupné z: https://dx.doi.org/10.1021/ct4007184.

@article{1127254,
   author = {Badri, Zahra and Pathak, Shubhrodeep and Fliegl, Heike and RashidiandRanjbar, Parviz and Bast, Radovan and Marek, Radek and Foroutannejad, Cina and Ruud, Kenneth},
   article_location = {Washington},
   article_number = {11},
   doi = {http://dx.doi.org/10.1021/ct4007184},
   keywords = {Ring Current Model; Magnetizability; All-Metal Aromaticity; DFT; MCSCF},
   language = {eng},
   issn = {1549-9618},
   journal = {Journal of Chemical Theory and Computation},
   title = {All–Metal Aromaticity: Revisiting the Ring Current Model among Transition Metal Clusters},
   url = {http://dx.doi.org/10.1021/ct4007184},
   volume = {9},
   year = {2013}
}

TY  - JOUR
ID  - 1127254
AU  - Badri, Zahra - Pathak, Shubhrodeep - Fliegl, Heike - Rashidi-Ranjbar, Parviz - Bast, Radovan - Marek, Radek - Foroutannejad, Cina - Ruud, Kenneth
PY  - 2013
TI  - All–Metal Aromaticity: Revisiting the Ring Current Model among Transition Metal Clusters
JF  - Journal of Chemical Theory and Computation
VL  - 9
IS  - 11
SP  - 4789-4796
EP  - 4789-4796
PB  - American Chemical Society
SN  - 15499618
KW  - Ring Current Model
KW  - Magnetizability
KW  - All-Metal Aromaticity
KW  - DFT
KW  - MCSCF
UR  - http://dx.doi.org/10.1021/ct4007184
L2  - http://dx.doi.org/10.1021/ct4007184
N2  - We present new insight into the nature of aromaticity in metal clusters. We give computational arguments in favor of using the ring-current model over local indices, such as nucleus independent chemical shifts, for the determination of the magnetic aromaticity. Two approaches for estimating magnetically induced ring currents are employed for this purpose; one based on the quantum theory of atoms in molecules (QTAIM) and the other where magnetically–induced current densities (MICD) are explicitly calculated. We show that the two–zone aromaticity/antiaromaticity of a number of 3d metallic clusters (Sc3–, Cu3+, and Cu42–) can be explained using the QTAIM–based magnetizabilities. The reliability of the calculated atomic and bond magnetizabilities of the metallic clusters are verified by comparison with MICD computed at the multiconfiguration self–consistent field (MCSCF) and density functional levels of theory. Integrated MCSCF current strength susceptibilities as well as a visual analysis of the calculated current densities confirm the interpretations based on the QTAIM magnetizabilities. In view of the new findings, we suggest a simple explanation based on classical electromagnetic theory to explain the anomalous magnetic shielding in different transition metal clusters. Our results suggest that the nature of magnetic aromaticity/antiaromaticity in transition–metal clusters should be assessed more carefully based on global indices.
ER  -

BADRI, Zahra, Shubhrodeep PATHAK, Heike FLIEGL, Parviz RASHIDI-RANJBAR, Radovan BAST, Radek MAREK, Cina FOROUTANNEJAD a Kenneth RUUD. All–Metal Aromaticity: Revisiting the Ring Current Model among Transition Metal Clusters. \textit{Journal of Chemical Theory and Computation}. Washington: American Chemical Society, 2013, roč.~9, č.~11, s.~4789-4796. ISSN~1549-9618. Dostupné z: https://dx.doi.org/10.1021/ct4007184.

Podrobný výpis o publikaci