reading an interview with her or something when The Time of Angels/Flesh and Stone came out, and she did say something to the effect of not wanting to flirt as much with Matt Smith because he was so much younger than her and she didn't want River to come off as a cougar. I don't think his Doctor seems that young when he's in character anyway, but it's understandable.
Makes sense, I suppose. But you're right that Matt Smith does a good job of seeming a lot older than he is.
In a more meta/continuity approach, the River we've been seeing this season is apparently much younger than the River we met in the Library, so perhaps her different attitude can be attributed to that she's in a different place in her life. 

Perhaps... I can see that.
soilent brad is PEOPLE!
1 + 2 + 3 + 4 + 5 = EM2C <-- Define it!
"Uh...we don't support the Hannah Montana empire."
- My 6 year old niece
1 + 2 + 3 + 4 + 5 = EM2C <-- Define it!
"Uh...we don't support the Hannah Montana empire."
- My 6 year old niece
/Doctor Who: new trailer
20/01/2011 10:24:10 PM
- 775 Views
The Doctor in America makes me feel patriotic.
20/01/2011 10:33:21 PM
- 580 Views

Re: The Doctor in America makes me feel patriotic.
20/01/2011 10:44:04 PM
- 602 Views

Have we a start date yet? *NM*
21/01/2011 04:05:59 AM
- 318 Views
No, but it is expected to be earlier than the last couple of years
21/01/2011 05:13:07 PM
- 573 Views
Saw this after watching the Christmas Special.
21/01/2011 06:42:20 PM
- 660 Views
Re: Saw this after watching the Christmas Special.
21/01/2011 06:43:51 PM
- 625 Views
Awesome
22/01/2011 08:08:17 PM
- 497 Views

Re: Awesome
22/01/2011 08:09:38 PM
- 540 Views

Thing is...
22/01/2011 08:21:29 PM
- 583 Views
Re: Thing is...
22/01/2011 08:22:38 PM
- 652 Views
Re: Thing is...
22/01/2011 08:44:16 PM
- 642 Views