Charles B. Musgrave - Assistant Professor

Office: Keck Science Building, Room 261
Phone: (650) 725-9176
FAX: (650) 725 7294
E-Mail: chasm@stanford.edu
Admin. Associate: Victoria Lee, (650)723-7503

Highest Degree

• Ph.D., California Institute of Technology, 1994

Major Honors and Awards

• Feynman Prize in Nanotechnology (1993)

Research Area

Our research program focuses on using quantum mechanics to simulate molecular processes in important engineering problems. Our approach is fundamental and interdisciplinary and combines quantum mechanics, chemical kinetics, and surface and materials chemistry. We aim to develop a fundamental molecular and mechanistic understanding of the processes underlying important new technologies and to establish quantum simulations as an engineering tool for molecular level computational prototyping and design. Problems we investigate include ALD, the design of homogeneous transition metal catalysts and dyes for dye-sensitized solar cells, solid oxide fuel cells, and interfaces between semiconductors and organic and biological molecules.

Atomic Layer Deposition

ALD is a process that has recently gained enormous attention. It involves exposure of surfaces to alternating pulses of different precursors to form atomic layers of deposited material. We focus on using QM simulations to determine the chemical mechanisms that govern ALD. Our work has pioneered the use of QM simulation to study ALD and has resulted in the most detailed pictures of ALD for several important systems. Our ultimate goal is to create a fundamental framework of principles that supports the rational development of new ALD processes.

Ab Initio Design of Transition Metal Catalysts

We use QM simulations to understand how the electronic environment of the metal center affects the properties of the catalyst. Our work investigating the catalytic polymerization of polyethylene-polystyrene block co-polymers led to the ab initio design of a better, novel pendant ligand Ti-TEMPO catalyst (with R. Waymouth). We also simulated the conversion of methane into methanol using cisplatin and Catalytica. We then used the resulting principles to design a new catalyst that exceeds the abilities of existing complexes and meets performance targets for practical implementation. We have also simulated the enantioselective ring-opening of epoxides by Co-Salen (with E. Jacobsen of Harvard). The key transition state is bimolecular in Co-Salen and thus computationally challenging due to its size and complexity. From these simulations we discovered the source of Co-Salen’s enantioselectivity.

De Novo Design of Solar Cells

We use time-dependent DFT to determine the electronic energy levels of dyes to predict their photo absorption spectra. Our goal is to replace the traditional trial and error approach to dye design with a rational design approach to discover dyes for more efficient photovoltaics. We also are using QM simulation to design improved organic and quantum dot photovoltaic materials and molecules which facilitate fast electron transfer across photovoltaic interfaces.

Solid Oxide Fuel Cells

We use quantum simulations to investigate atomistic processes in solid-oxide fuel cells with the aim of designing improved electrolytes and catalysts. We have simulated the oxygen anion conduction in yttria stabilized zirconia and have developed a detailed picture of what governs YSZ conductivity. These results enable us to suggest new electrolyte materials with improved properties that we then study by simulation.

Semiconductors And Organic And Biological Molecules Interfaces

We study how various organic molecules react on semiconductor surfaces and have developed the most comprehensive theoretical description of organic reactions on semiconductors. We are extending this work by investigating the unique electronic properties of the interfaces formed between organics and semiconductors and by investigating reactions of biological molecules with semiconductors. We have recently found several interesting new types of reactions between amino acids and semiconductor surfaces, which may potentially lead to new types of electrical junctions in molecular electronics.

Several Recent Publications

1. Huang, K., J. Han, A. Cole, C. Musgrave and R. Waymouth, “Homolysis of Weak Ti-O Bonds: Experimental and Theoretical Studies of Titanium Oxygen Bonds Derived from Stable Nitroxyl Radicals,” Journal of the American Chemical Society, 127, 3807-3816 (2005).
2. Xu, Y. and C. Musgrave, “Atomic Layer Deposition of Hafnium Nitrides Using Ammonia and Alkylamide Precursors,” Chemical Physics Letters, 407, 272-275 (2005).
3. Mui, C. and C. Musgrave, “Thermal Nitridization of the Ge(100) 2x1 Surface By Ammonia,” Langmuir, 21, 5230-5232 (2005).
4. Xu, Y. and C. Musgrave, “Atomic Layer Deposition of HfO2 on Nitridized Si Surfaces,” Applied Physics Letters, 86, 192110-192113 (2005).
5. Xu, Y. and C. Musgrave, “A Chemical Mechanism for Nitrogen Incorporation Into HfO2 ALD Films Using Ammonia and Alkylamides as Precursors,” Surface Science, 591, L280-L285 (2005).
6. Pornprasertsuk, R., P. Ramanarayanan, C. Musgrave and F. Prinz, “Predicting Ionic Conductivity of Solid Oxide Fuel Cell Electrolytes from First Principles,” Journal of Applied Physics, 98, 1-8 (2005).
7. Mukhopadhyay, A. and C. Musgrave, “Non-Growth Ligand Exchange Reactions in Atomic Layer Deposition of HfO2,” Chemical Physics Letters, 421, 215-220 (2006).
8. Mukhopadhyay, A., J. Sanz and C. Musgrave, “First-Principles Calculations of Structural and Electronic Properties of Monoclinic Hafnia Surfaces,” Physical Review B, 73, 115330-115337 (2006).
9. Huang, K., J. Han, C. Musgrave, and R. Waymouth, “Density Functional Theory Calculations on Ti-TEMPO complexes: Influence of Ancillary Ligation on the Strength of the Ti-O bond,” Organometallics, 25, 3317-3323 (2006).
10. Mukhopadhyay, A., J. Sanz and C. Musgrave, “First-Principles Investigation of Hydroxylated Monoclinic HfO2 Surfaces,” Chemistry of Materials, 18, 3397-3403 (2006).
11. Paul, A. and C. Musgrave, “A Detailed Theoretical Study of the Mechanism and Energetics of Methane to Methanol Conversion by Cis-Platin and Catalytica,’ Organometallics, In press, 2006.
12. Ardalan, P., N. Davani and C. Musgrave, “ The Attachment of Alanine and Arginine to the Ge(100)-2x1 Surface,” In press, 2006.
13. Huang, K., J. Han, C. Musgrave, and E. Fujita, “Carbon Dioxide Reduction by Pincer Rhodium ?2-Dihydrogen Complexes: Hydrogen Binding Modes and Mechanistic Studies by Density Functional Theory Calculations,” Submitted to Organometallics, In press, 2006.

Current Students, Research Associates and Faculty

Ph.D. Students

• Chris McCormick (UCLA)—Transition Metal Catalysis For Fuel Cells
• Paul Zimmerman (UC Berkeley)—Channel Materials To Overcome Kt/Q Limitations
• Pendar Ardulan (Sharif University, Iran - with S. Bent)—Atomic Layer Deposition Of Metals
• Chenyu Wang (Tsinghua, China)—Quantum Simulations Of Quantum Dot Solar Cells

Postdocs

• Dr. Ankan Paul (University of Georgia)—De Novo Design Of Transition Metal Catalysts
• Dr. Atashi Mukhopadhyay (Univeristy of Cologne, Germany)—Atomic Layer Deposition And Interfaces With High-K Materials

Research Associate

• Dr. Zhiyong Zhang—High-K Interfaces and DNA Sensing with Quantum Dots

Visiting Faculty

• Professor Javier Fernandez Sanz (on sabbatical from—Atomic Layer Deposition and Interfaces with High-K Materials