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A Quantum Chemical View of Molecular and Nano-Electronics
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
2007 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

This dissertation presents a generalized quantum chemical approach for electron transport in molecular electronic devices based on Green's function scattering theory. It allows to describe both elastic and inelastic electron transport processes at first principles levels of theory, and to treat devices with metal electrodes either chemically or physically bonded to the molecules on equal footing. Special attention has been paid to understand the molecular length dependence of current-voltage characteristics of molecular junctions. Effects of external electric fields have been taken into account non-perturbatively, allowing to treat electrochemical gate-controlled single molecular field effect transistors for the first time. Inelastic electron tunneling spectroscopy of molecular junctions has been simulated by including electron-vibration couplings. The calculated spectra are often in excellent agreement with experiment, revealing detailed structure information about the molecule and the bonding between molecule and metal electrodes that are not accessible in the experiment.

An effective central insertion scheme (CIS) has been introduced to study electronic structures of nanomaterials at first principles levels. It takes advantage of the partial periodicity of a system and uses the fact that long range interaction in a big system dies out quickly. CIS method can save significant computational time without loss of accuracy and has been successfully applied to calculate electronic structures of one- , two- , and three-dimensional nanomaterials, such as sub-116 nm long conjugated polymers, sub-200nm long single-walled carbon nanotubes, sub-60 base pairs DNA segments, nanodiamondoids of sub-7.3nm in diameter and Si-nanoparticles of sub-6.5nm in diameter at the hybrid density functional theory level. The largest system under investigation consists of 100,000 electrons. The formation of energy bands and quantum confinement effects in these nanostructures have been revealed. Electron transport properties of polymers, SWCNTs and DNA have also been calculated.

Place, publisher, year, edition, pages
Stockholm: KTH , 2007. , 70 p.
National Category
Biochemistry and Molecular Biology
Identifiers
URN: urn:nbn:se:kth:diva-4335ISBN: 978-91-7178-618-0 (print)OAI: oai:DiVA.org:kth-4335DiVA: diva2:11858
Public defence
2007-04-24, FA32, AlbaNova, Roslagstullsbacken, Stockholm, 14:00
Opponent
Supervisors
Note
QC 20100729. Ändrat felaktig titel "Theoretical Chemistry, Molecular and Nano-electronics" 20100729.Available from: 2007-04-17 Created: 2007-04-17 Last updated: 2010-07-30Bibliographically approved
List of papers
1. A generalized quantum chemical approach for elastic and inelastic electron transports in molecular electronics devices
Open this publication in new window or tab >>A generalized quantum chemical approach for elastic and inelastic electron transports in molecular electronics devices
2006 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 124, no 3, 034708-1-034708-10 p.Article in journal (Refereed) Published
Abstract [en]

A generalized quantum chemical approach for electron transport in molecular devices is developed. It allows one to treat devices where the metal electrodes and the molecule are either chemically or physically bonded on equal footing. An extension to include the vibration motions of the molecule has also been implemented which has produced the inelastic electron-tunneling spectroscopy of molecular electronics devices with unprecedented accuracy. Important information about the structure of the molecule and of metal-molecule contacts that are not accessible in the experiment are revealed. The calculated current-voltage (I-V) characteristics of different molecular devices, including benzene-1,4-dithiolate, octanemonothiolate [H(CH2)(8)S], and octanedithiolate [S(CH2)(8)S] bonded to gold electrodes, are in very good agreement with experimental measurements.

Keyword
Current voltage characteristics; Electrodes; Electron tunneling; Spectroscopic analysis; Gold electrodes; Molecular devices; Molecular electronics devices; Vibration motions; Quantum theory
National Category
Biochemistry and Molecular Biology
Identifiers
urn:nbn:se:kth:diva-6982 (URN)10.1063/1.2159490 (DOI)000234757400042 ()2-s2.0-31144451119 (Scopus ID)
Note
QC 20100730Available from: 2007-04-17 Created: 2007-04-17 Last updated: 2017-12-14Bibliographically approved
2. An elongation method for first principle simulations of electronic structures and electron transport properties of finite nanostructures
Open this publication in new window or tab >>An elongation method for first principle simulations of electronic structures and electron transport properties of finite nanostructures
2006 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 124, no 21, 214711- p.Article in journal (Refereed) Published
Abstract [en]

An effective elongation method has been developed to study electronic structures and electron transport properties of nanoelectronic and bioelectronic devices at a hybrid density functional theory level. It enables to treat finite nanostructures consisting of as many as 28 000 electrons and has been successfully applied to sub-120-nm-long conjugated polymers, sub-60-nm-long single-walled carbon nanotubes, and 30 base-pair DNA molecules. The calculated current-voltage characteristics of different systems are found to be in good agreement with the experiments. Some unexpected behaviors of these nanosized devices have been discovered.

Keyword
Carbon nanotubes; Computer simulation; Current voltage characteristics; DNA; Electron transport properties; Electronic structure; Organic polymers; Probability density function; Density functional theory; Finite nanostructures; Nanosized devices; Nanostructured materials
National Category
Biochemistry and Molecular Biology
Identifiers
urn:nbn:se:kth:diva-6983 (URN)10.1063/1.2207137 (DOI)000238758700044 ()2-s2.0-34547853644 (Scopus ID)
Note
QC 20100730Available from: 2007-04-17 Created: 2007-04-17 Last updated: 2017-12-14Bibliographically approved
3. An efficient first-principle approach for electronic structures calculations of nanomaterials
Open this publication in new window or tab >>An efficient first-principle approach for electronic structures calculations of nanomaterials
Show others...
2008 (English)In: Journal of Computational Chemistry, ISSN 0192-8651, E-ISSN 1096-987X, Vol. 29, no 3, 434-444 p.Article in journal (Refereed) Published
Abstract [en]

An efficient parallel implementation has been realized for a recently proposed central insertion scheme (Jiang, Liu, Lu, Luo. J Chem Phys 2006,124,214711; J Chem Phys 2006,125, 149902) that allows to calculate electronic structures of nanomaterials at various density functional theory levels. It has adopted the sparse-matrix format for Fock/Kohn-Sham and overlap matrices, as well as a combination of implicitly restarted Arnoldi methods (IRAM) and spectral transformation for computing selected eigenvalues/eigenvectors. A systematic error analysis and control for the proposed method has been provided based on a strict mathematical basis. The efficiency and applicability of the new implementation have been demonstrated by calculations of electronic structures of two different nanomaterials consisting of one hundred thousand electrons.

Keyword
nanomaterials; density functional theory; electronic structures; carbon nanotubes; diamondoids
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-6984 (URN)10.1002/jcc.20799 (DOI)000252864500011 ()2-s2.0-38349153574 (Scopus ID)
Note
QC 20100726Available from: 2007-04-17 Created: 2007-04-17 Last updated: 2017-12-14Bibliographically approved
4. Length dependence of coherent electron transportation in metal-alkanedithiol-metal and metal-alkanemonothiol-metal junctions
Open this publication in new window or tab >>Length dependence of coherent electron transportation in metal-alkanedithiol-metal and metal-alkanemonothiol-metal junctions
2004 (English)In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448, Vol. 400, no 4-6, 336-340 p.Article in journal (Refereed) Published
Abstract [en]

We have applied the elastic-scattering Green's function theory to study the coherent electron transportation processes in both metal-alkanedithiol-metal (gold-[S(CH2)(n)S]-gold, n = 8-14) and metal-alkanemonothiol-metal (gold-[H(CH2)(n)S]-gold, n = 814) at the hybrid density functional theory level. It is shown that the current decreases exponentially with the molecular length. At the low temperature limit the electron decay rate, beta, for alkanedithiol junction is found to be around 0.30/CH2 at 1.0 V bias, much smaller than the calculated value of 0.60/CH2 for alkanemonothiol junction. The decay rate for alkanedithiol junction at the room temperature is neither sensitive to the activation of the Au-S stretching vibrational mode nor to the external bias. The calculated current-voltage characteristics and decay rates for both junctions are in excellent agreement with the corresponding experimental results.

Keyword
alkane derivative; dithiol derivative; article; density functional theory; elasticity; electron transport; low temperature; molecular dynamics; room temperature
National Category
Biochemistry and Molecular Biology
Identifiers
urn:nbn:se:kth:diva-6985 (URN)10.1016/j.cplett.2004.10.136 (DOI)000225906300012 ()2-s2.0-10344228738 (Scopus ID)
Note
QC 20100730Available from: 2007-04-17 Created: 2007-04-17 Last updated: 2017-12-14Bibliographically approved
5. Electron transport in self-assembled polymer molecular junctions
Open this publication in new window or tab >>Electron transport in self-assembled polymer molecular junctions
Show others...
2006 (English)In: Physical Review Letters, ISSN 0031-9007, E-ISSN 1079-7114, Vol. 96, no 2, 027801- p.Article in journal (Refereed) Published
Abstract [en]

A molecular junction of a poly(p-phenyleneethynylene)s derivative with thioacetate end groups (TA-PPE) was fabricated by self-assembling. Nanogap electrodes made by electroplating technique was used to couple thiol end groups of TA-PPE molecules. Room temperature current-voltage characteristics of the molecular junction exhibited highly periodic, repeatable, and identical stepwise features. First-principles calculations suggest that one possibility for the equidistant step is due to the opening of different conducting channels that corresponds to the unoccupied molecular orbitals of the polymer in the junction. It is interesting to see that an 18 nm long polymer is of quantized electronic structures and behaves like a quantum transport device.

Keyword
Electrodes; Electroplating; Molecular dynamics; Nanostructured materials; Polymers; Self assembly; Current-voltage; Molecular junction; Quantized electronic structures; Thioacetate end groups (TA-PPE); Electron transport properties
National Category
Biochemistry and Molecular Biology
Identifiers
urn:nbn:se:kth:diva-6986 (URN)10.1103/PhysRevLett.96.027801 (DOI)000234758100098 ()2-s2.0-32644481386 (Scopus ID)
Note
QC 20100730. Titeln ändrad från "Coherent electron transport in self-assembled conjugated polymer molecular junctions".Available from: 2007-04-17 Created: 2007-04-17 Last updated: 2017-12-14Bibliographically approved
6. Quantum confinement in nano-diamondoids
Open this publication in new window or tab >>Quantum confinement in nano-diamondoids
(English)In: Physical Review Letters, ISSN 0031-9007, E-ISSN 1079-7114Article in journal (Other academic) Submitted
National Category
Biochemistry and Molecular Biology
Identifiers
urn:nbn:se:kth:diva-6987 (URN)
Note
QS 20120327Available from: 2007-04-17 Created: 2007-04-17 Last updated: 2017-12-14Bibliographically approved
7. First-principles simulations of inelastic electron tunneling spectroscopy of molecular electronic devices
Open this publication in new window or tab >>First-principles simulations of inelastic electron tunneling spectroscopy of molecular electronic devices
2005 (English)In: Nano letters (Print), ISSN 1530-6984, E-ISSN 1530-6992, Vol. 5, no 8, 1551-1555 p.Article in journal (Refereed) Published
Abstract [en]

Inelastic electron tunneling spectroscopy (IETS) is a powerful experimental tool for studying the molecular and metal contact geometries in molecular electronic devices. A first-principles computational method based on the hybrid density functional theory is developed to simulate the IETS of realistic molecular electronic devices. The calculated spectra of a real device with an octanedithiolate embedded between two gold contacts are in excellent agreement with recent experimental results. Strong temperature dependence of the experimental IETS spectra is also reproduced. It is shown that the IETS is extremely sensitive to the intramolecular conformation and the molecule-metal contact geometry changes. With the help of theoretical calculations, it has finally become possible to fully understand and assign the complicated experimental IETS and, more importantly, provide the structural information of the molecular electronic devices.

Keyword
Computer simulation; Electron tunneling; Probability density function; Spectroscopy; Thermal effects; Inelastic electron tunneling spectroscopy (IETS); Intramolecular conformations; Molecular electronic devices; Structural information; article; chemical model; chemistry; computer simulation; electronics; equipment; evaluation; feasibility study; materials testing; methodology; scanning tunneling microscopy; spectroscopy; Computer Simulation; Electronics; Equipment Failure Analysis; Feasibility Studies; Materials Testing; Microscopy, Scanning Tunneling; Models, Chemical; Nanostructures; Spectrum Analysis
National Category
Biochemistry and Molecular Biology
Identifiers
urn:nbn:se:kth:diva-6988 (URN)10.1021/nl050789h (DOI)000231211300005 ()2-s2.0-24344435119 (Scopus ID)
Note
QC 20100730. Titeln ändrad från "First-principles simulations of inelastic electron tunneling spectroscopy of molecular junctions"Available from: 2007-04-17 Created: 2007-04-17 Last updated: 2017-12-14Bibliographically approved
8. Probing molecule-metal bonding in molecular junctions by inelastic electron tunneling spectroscopy
Open this publication in new window or tab >>Probing molecule-metal bonding in molecular junctions by inelastic electron tunneling spectroscopy
2006 (English)In: Nano letters (Print), ISSN 1530-6984, E-ISSN 1530-6992, Vol. 6, no 8, 1693-1698 p.Article in journal (Refereed) Published
Abstract [en]

We present first-principles calculations for the inelastic electron tunneling spectra ( IETS) of three molecules, 1-undecane thiol (C11), alpha, omega-bis(thioacetyl)oligophenylenethynylene (OPE), and alpha,omega-bis(thioacetyl) oligophenylenevinylene (OPV), sandwiched between two gold electrodes. We have demonstrated that IETS is very sensitive to the bonding between the molecule and electrodes. In comparison with experiment of Kushmerick et al. (Nano Lett. 2004, 4, 639), it has been concluded that the C11 forms a strong chemical bond, while the bonding of the OPE and OPV systems are slightly weaker. All experimental spectral features have been correctly assigned.

Keyword
Chemical bonds; Electrodes; Electron tunneling; Organic compounds; First principles calculations; Inelastic electron tunneling spectra (IETS); Molecular junctions; Molecule-metal bonding; article; binding site; chemical model; chemical structure; chemistry; computer simulation; elasticity; electron transport; energy filtered transmission electron microscopy; methodology; microelectrode; scanning tunneling microscopy; Binding Sites; Computer Simulation; Elasticity; Electron Transport; Metals; Microelectrodes; Microscopy, Energy-Filtering Transmission Electron; Microscopy, Scanning Tunneling; Models, Chemical; Models, Molecular; Nanostructures; Polymers
National Category
Biochemistry and Molecular Biology
Identifiers
urn:nbn:se:kth:diva-6989 (URN)10.1021/nl060951w (DOI)000239623900021 ()2-s2.0-33748329697 (Scopus ID)
Note
QC 20100730Available from: 2007-04-17 Created: 2007-04-17 Last updated: 2017-12-14Bibliographically approved
9. First-principles study of electrochemical gate-controlled conductance in molecular junctions
Open this publication in new window or tab >>First-principles study of electrochemical gate-controlled conductance in molecular junctions
2006 (English)In: Nano letters (Print), ISSN 1530-6984, E-ISSN 1530-6992, Vol. 6, no 9, 2091-2094 p.Article in journal (Refereed) Published
Abstract [en]

A first-principles computational method is developed to study the electrochemical gate-controlled conductance in molecular junctions. It has been applied to a single molecular field-effect transistor made by a perylene tetracaboxylic diimide molecule connected to gold electrodes and has successfully reproduced the experimentally observed huge gate voltage effect on the current. It is found that such a significant gain is a result of the large polarization of the molecule induced by the huge local electrical field generated by the electrochemical gate. The resonant electron tunneling through unoccupied molecular orbitals is shown to be the dominant transport process.

Keyword
Gold electrodes; Molecular junctions; Molecular orbitals; Resonant electron tunneling; Computational methods; Electric fields; Electrochemistry; Electron tunneling; Field effect transistors; Molecular dynamics; Computer Simulation; Electric Conductivity; Electrochemistry; Equipment Design; Equipment Failure Analysis; Microelectrodes; Models, Chemical; Models, Molecular; Nanostructures; Transistors
National Category
Biochemistry and Molecular Biology
Identifiers
urn:nbn:se:kth:diva-6990 (URN)10.1021/nl061376z (DOI)000240465100045 ()16968031 (PubMedID)2-s2.0-33749680460 (Scopus ID)
Note
QC 20100730Available from: 2007-04-17 Created: 2007-04-17 Last updated: 2017-12-14Bibliographically approved

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