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Importance of Pd and Pt excited states in N 2 O capture and activation: A comparative study with Rh and Au atoms
Nitrous oxide (N 2 O) is an intermediate compound formed during catalysis occurring in automobile exhaust pipes. In this work, the N 2 O capture and activation by Pt and Pd atoms in the ground and excited states of many multiplicities are studied. Pt and Pd + N 2 O reactions are studied at multirefe...
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Published in: | International journal of quantum chemistry 2013-07, Vol.113 (13), p.1794-1802 |
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Main Authors: | , , , , |
Format: | Article |
Language: | English |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | Nitrous oxide (N
2
O) is an intermediate compound formed during catalysis occurring in automobile exhaust pipes. In this work, the N
2
O capture and activation by Pt and Pd atoms in the ground and excited states of many multiplicities are studied. Pt and Pd + N
2
O reactions are studied at multireference second‐order perturbation level of theory using
C
s
symmetry. The PtN
2
O (
1
A′,
5
A′, and
5
A″) species are spontaneously created from excited states. Only the
5
A′ and
5
A″ states exhibit N
2
O activation reaction paths when N
2
O approaches Pt end‐on by the N or O atoms side or side‐on yielding NO or N
2
as products, respectively. Pt
+
cations ground and excited states, capture N
2
O, although only Pt
+
(
6
A′ and
6
A″) states show N
2
O activation yielding O and N
2
as products. In the Pd atom case, PdN
2
O (
1
A′ and
5
A″) species are also spontaneously created from excited states. The
5
A″ state exhibits N
2
O activation yielding N
2
+ O as products. Pd
+
cations in both ground and excited states capture N
2
O; however, only the [PdN
2
O]
+
(
4
A′,
4
A″,
6
A′, and
6
A″) states in side‐on approaches and (
6
A′) in end‐on approach activate the N
2
O and yield the N
2
bounded to the metal and O as product. The results obtained in this work are discussed and compared with previous calculations of Rh and Au atoms. The reaction paths show a metal–gas dative covalent bonding character. Löwdin charge population analyses for Pt and Pd active states show a binding done through charge donation and retrodonation between the metals and N
2
O. © 2013 Wiley Periodicals, Inc. |
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ISSN: | 0020-7608 1097-461X |
DOI: | 10.1002/qua.24405 |